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879 LXXX.-Contributions to t h e Chemistry of t h e Cerite Metals. 111. By B. BRAUNER, Ph.D., P.C.S., late Berkeley Fellow of the Owens College, Adjunct and Privatdocent in the Bohemian University, Prague. Introductory Remarks. I N a paper published several years ago (Chem. Xoc. J., Trans., 1882,68, and in extenso, Monatsli. Chem., 1882, 1-60), I endeavoured to deter- mine the position of the cerite metals in the periodic system of elements, and arranged them in the order- CeiV. Djiii-v. 139 141-6 146.6 A little later (Monatsh. Cliern., 1882, 486, and Trans., 1883, 278), I succeeded in proving that the didymium from cerite is a nziz- ture, and that the atomic weight of the true didymium is a t most Di = 145.4. For lanthanum I found a t the same time the number La = 138.28. Working with a more abundant supply of the rare material, Cleve, whilst confirming my number for lanthanum, that is, 138.28 (BuZl.SOC. Chirn., 39, 251, 289), found didymium to be Di = 142.3-142.4. If, as has hitherto been the case, the number found for the atomic weight of cerium by Biihrig (J. pr. Chem. 120, 222), namely, Ce = 141.6, be admitted to represent the truth, the order of the atomic weights of the said elementsin the system would be as follows :- La. Ce. Di. 138.2 141.6 142.3 L-.---JL- ----J Difference.. . . 3.4 0.7 It must be admitted that the lanthanum and didymium preparations with which Cleve determined the atomic weights of these elements were pure and homogeneous, and, as the method used by him does not involve any apparent source of error, we are justified in regarding his numbers as very nearly representing the truth.It is, however, very evident that the difference between the atomic weights of ]antha- niim and cerium (3.4) is much larger than that between cerium and didymium (0.7), and the question therefore arose whether Biihrig’s number (Ce = 141.6) is really the atomic weight of cerium, as is generally believed, especially as Wolf (XiZZ. Anzer. J. [2], 46, 53- 62) has found the atomic weight of thepurest cerium to be Ce = 137,880 BRAUNER : CONTRIBUTIONS TO THE a much lower number than Biihrig’s. tigation is to answer this question. The object of the present inves- Historical Review. Since 1816, the atomic weight of cerium has been determined by many chemists, but the numbers found, especially those which seem to be the most trustworthF, differ more widely from each other than niight be expected.The following is a short review of the determi- iiations made. For details I must refer partly to the origiual papers, 1)artly to the works recently published by G. F. Becker (Constants of LVature: Part IV, Washington, 1880); F. W. Clarke (Constants qf Nature, Part V, Washington, 1882); Lothar Bieyer and Seubert (Die Atomgewichte der Elemente, Lcipzig, 1883) ; and by Ostwald (Lehrbuch der Allgemeiiien Chemie, Leipzig, 1884). My comments on the individual determinations form a special chapter of the present paper. I should state that I call the oxide CezO, and its salts cerous, and the oxide CeOz ceric and not cerium peroxide, as is done by some chemists, as the latter name must be reserved for the oxide Ce03, recently investigated by L.de Boisbaudran (Conzpt. rend., 100, 605), and Clew (Bull. SOC. Chinz., 43, 5 3 ) . The numbers below refer to 0 = 16. The number to be deduced from Hisinger’s (Bchweig., 17, 424 ; Pogg. An?&., 8, 186) experiments, made in 1814-16, is Ce = 137.9. The method is not given, and his cerium mas contaminated with lan- thanum and didymium, the existence of the last, two elements not being known a t that time. Beringer’s (Annalm, 42,134) ceri urn salts were also rose-coloured. The numbers obtained by him were Ce = 142.3 from tlie relation of ceric oxide to silver chloride ; Ce = 142.3 from t1:at of ceric oxide to barium sulphate ; and Ce = 141.6 from the combustion of cerous forniate.Rammelsberg’s (Pogg. Ann., 55, 6 5 ) analysis of anhydrous cerous sulphate, made in 1842, gives Ce = 154.3. Hermann (J. p r . Cliein.. 30, 184) in 1843, determined the relation of anhydrous cerous sulphate to barium sulpbate. His numbers give Ce = 139.4. FromMarignac’s (Ann. Clhn. Phys. [3], 27,209 ; Arch. Sci. Ph. Nut. [ 11, 8, 273) volumetric analysis of cerous sulphate solutions by means of barium chloride, it follows that Ce = 141.8 ; whilst the relation of anhydrous cerous sulphate to bsyium sulphitte, Ce is 141.6. Later on (Ann. Chinz. Phys. [3], 38, 148), the same chemist gave the pre- ference to the number Ce = 137.7, but without giving any experi- meiitd e 1-idence.CHEMISTRS OF TRE CERITE METALS. 881 Jegel, in 1858 (Annalen, 105, 45), deduced the number Ce = 1381, from the combustion of cerous oxalate.An analysis of the sulphate gave Ce = 137.8. I n both cases, the ceric oxide was analyseil iodo- metrically. Lothar Meyer and Seubert calculate, instead of the above num- bers, Ce = 137.4 and 138.3. A combustion of the oxalate, made by Rammelsberg (Pogg. Ann., 108,44) in 1859, gave Ce = 138.1. All the above determinations were made with cerium preparations containing larger or smaller quantities of foreign earths, for the ceric oxide obtained was more or less brown coloured. In 1867, an extended investigation of the subject was undertaken by C. Wolf (Zoc. cit.) in Bunsen’s laboratory, but unfortunately, it remained unfinished in consequence of his premature death, and has, up to the present, never been again taken up.The following details from Wolf’s diary, pub- lished after his death by Genth, may be given here, as being important in relation to the present question. Ceric nitrate prepared from the crude oxides, was decomposed by pouring its aqueous solution into boiling water containing some sul- phuric acid, and the precipitate of basic nitrate and sulphate, N, was converted into cerous sulphate. This was recrystallised at least ten times. Wolf heated the sulphate over a, small flame in a double platinum crucible, in order to determine the amount of water of crys- tallisation (by loss of weight), and from the aqueous solution of the anhydrous sulphnte thus obtained the oxalate was precipitated by a boiling concentrated solution of oxalic acid. This, by careful igni- tion, was converted into ceric oxide.In the filtrate, the sulphuric acid was determined as barium sulphate. The excess of oxygen in Ce02 ( Cez04) over Ce20s was determined iodometrically. From these four data (H,O, Ce02, Ce203, and SOs) the composition of the anhy- drous cerous sulphate was first calculated, and from this the equiva- lent of cerium. As the ceric oxide obtained in the first series of determinations had a, brownish colour, part of the precipitate N was purified by dis- solving and precipitating with boiling water; and in this way the precipitate N, was obtained. The sulphate obtained from it gave a much paler ceric oxide. The precipitates N,, N,,, and Ns were obtained by Wolf in the same way, and the colour of the oxide was in each case paler than in the preceding.Wolf calls the oxide from N7 aZrnost white, and that from Ns white. I t is a very remarkable circumstance that, after every purification, as the oxide became more nearlg white, the equivalent of cerium was fonnd to decrease. VOL. XLVII. 3 P882 BRAUNER : COKTRIBUTIONS TO THE I n Wolf’s original paper the following numbers are calculated for the equivalent of cerium :- I. 11. IV. V. 46-187 45.760 45.699 45.664 This multiplied by 3 would represent the atomic weight as- I. 11. IV. V. 138.561 137.280 137.097 136.992 If, according to Clarke, the atomic weight be calculated from the relation of Ce2(SOJ3 to 2Ce02, as involving the least experimental error, the following numbers will be obtained (for 0 = 16, S = 32.06) :- I. I I. IV. V. Ce = 139.64 138.27 138.04 138.00 From these experiments Wolf concluded that the remarkable dimi- nution of the atomic weight of cerium could not be due to the elimi- nation of didymium only, but that the first portions may have contained a foreign substance.Wing (SiZZ. Amer. J. [2], 49, 358), in 1870, repeated Wolis experi- ments and process of purification, without, however, going further, and hispurest material gave Ce = 137.85. From Wolf’s and Wing’s experiments Clarke calculates as a mean Ce = 138.039. Buhrig’s (Zoc. cit.) experiments made in 1875, with a material free from didymium, in which large quantities of cerons oxalate were analysed by combustion in a current of oxygen, gave a remarkably high number, namely Ce = 141.523 (Clarke). His ceric oxide varied from yellow to salmon colour.Later on I shall return to the objec- tions which he raised against the analysis of cerous sulphate. While my present investigation, which has occupied me for some time past, was in progress, H. Robinson (Proc. Roy. Soc., 37, 150) published his paper on the same subject. The purification of his cerium salts was effected by Gibbs’s method. The cerium solution, free from didymium, finally obtained, was precipitated with oxalic acid, and the air-dried oxaIate was converted into the chloride by heating it in a current of hydrogen chloride. The cerous chloride, free from water and hydrogen chloride, was analysed volumetrically with a silver solution, according to Stas’ method. As a mean of the results of seven experiments (reduced to a vacuum), Robinson found- Ce = 140.2593 (0 = 16) or Ce = 139.9035 (H = 1).This uumber, as I shall show later on, is to be considered exact, forOHEMISTRY OF THE CERITE METALS. 883 in the method used by Robinson, all possible experimental errors are reduced to a minimum ; but I have nevertheless continued my experi- ments for several reasons. Firstly, the method I have used is diffe- rent from that adopted by Robinson, and our experiments therefore mutually control each other. Secondly, Wolf's experiments challenge investigation as regards the homogeneous character of the material, and as Robinson did not touch this question, it was all the more necessary for me to devote my attention to it. Experience has shown, especially in the case of the rare earth metals, that the atomic weights, determined even by the most trustworthy methods, may differ by several units from the truth, if the material used consisted of a mixture of earths.The history of scandium, yttrium, didgmium, and erbium may be quoted as examples. Method of Investigation. I n the operations of dissolvhg, evaporating, and boiling, only such vessels were used as had been treated for some time beforehand with acids. The acids, viz., hydrochloric, nitric, and sulphuric, were distilled shortly before use from a platinum retort, and kept in well-stopped bottles of Bohemian glass. A platinum tube, 60 cm. in length, 2.5 cm. wide, and weighing 600 grams, was used as a condenser, and for tbis 1 am much indebted to the Royal Society for a grant from the Govern- ment Chant Fund. Distilled water was once redistilled by means of the same arrangement, and absolute alcohol was similarly treated, the first and last portions of the distillate being rejected.The filter- paper used was kept in contact with warm hydrochloric acid for some time, and then well washed. In weighing, a fine balance, made by Verbeeck and Peckholdt, of Dresden, was used. In order to prevent the very sensible effect of radiant heat during weighing, the balance was covered on all sides with thick flannel, so that only the scale could be seen. To make the scale more visible, light mag reflected npan it from the sides by mirrors, and a t night the light of distant gas flames was concentrated upon i t by lenses. If the method of vibrations be used in weighing, and the observation of the " point of rest" be often repeated, the weight of a body weighing about 50 grams may be determined accurately wiihin O*OOOr)l to r).OOUO3 gram.The platinum crucibles were weighed in small thin glass bottles, and a similar vessel with platinum was used as counterpoise. As the weight, of substance used was generally about 2 grams, rarely 5 grams, only a few small weights were used: in this way the errors of weighing were reduced to a minimum. The following was the true weight of the pieces used F 3 P Z884 BRAUNER : CONTRIBUTIONS TO THE 2 = 2.00006 1 = 0.99996 1’= 0.99996 l”= 1.00005 0.5 = 0.49978 0.2 = 0.19992 0.1 = 0.10001 0.1’ = 0~10001 0.05 = 0,04996 0.02 = 0.02012 0.01 = 0~01010 0’01’ = 0~01012 rider= 0.Ol.002 CeOz (sp. gr. = 6.7) = 0.000172 gram.Ce2(S04)3 (sp. gr. = 3.9) = 0.000303 gram. In order t o obtain pure cerium preparations, I proceeded as follows : -From 2600 grams of cerite, 1380 grams of crude oxides were ob- tained by the method described in a former paper. After dissolving the oxides in moderately concentrated nitric acid and removing the excess of acid by evaporation, the remaining syrup was dissolved in a little water. On pouring this into a large quantity of pure boiling water, almost the whole of the cerium present (about half of the weight of the crude oxides) was precipitated as basic ceric nitrate. This could be easily and quickly washed on a Bunsen funnel with boiling water containing a little nitric acid. I shall call this first pre- cipitate N. For further purification, instead of using sulphuric acid, as is generally done, nitric acid was employed.This has the great advan- tage over the old method, that the excess of acid can be very easily removed by evaporation from the solution. If the solution of the resulting ceric nitrate, which is now crystalline, be again poured into boiling water, the filtrate will contain, besides the impurities which we wish to remove, much less cerium in solution than when sulphuric acid is used. This almost neutral ceric nitrate dissolves easily in a very large quantity of water, without undergoing decomposition. This method, especially the removal of tlie excess of acid by evapo- ration, enabled me to carry the purification much further than Wolf was able to do. In using nitric acid, the quantity of cerium is dimi- nished far less rapidlj by each precipitation than is the case with sulphuric acid.Whilst Wolf could repeat the process of precipitation only five times, I could obtain, by repeating this tedious process withOHEMISTRY OF THE OERITE METALS. 885 a part of the first precipitate only, the following series of precipitates (N) and corresponding filtrates (F), the last being kept separate :- N N, Nz NS N, N5 Ns N7 N* Nil NlO Nl, F Fi Fz F S Fd F, F, F7 F, F, Fio Fii. Now the question arose which cerium compounds were to be used for the atomio weight determination. After long deliberation, 1 chose the anhydrous cerous snlphate, as-with the exception of cerous chloride, which H. Robinson had succeeded in preparing only after my experiments were in progress-cerium does not form any other compound of definite composition suitable for the purpose.Buhrig rejected cerous sulphate-firstly, because the salt retains free sul- phuric wid from the mother-liquor so energetically that it cannot be fi-eed from i t even by repeated crystallisations ; secondlg, because he could not obtain the anhydrous sulphate, the salt retaining traces of water at a moderate heat, and undergoing partial decomposition when heated to incipient redness ; and thirdly, he remarks, that on preci- pitating the solution of the sulphate with barium chloride and after- wards with oxalic acid, the barium sulphate thrown down cont.ains cerium; whilst the cerium oxalttte, on the other hand, contains barium, but he does not consider that, if the analysis is to be made by precipitation at all, the process may be executed in the inverse order, without fear of committing the above errors.The first source of error was avoided in the following way:- Cerous snlphate, prepared by dissolving baRic cerie nitrate i n dilute sulphuric wid and sulphurous acid, and evaporating the solution in a platinum basin, was heated for some time in a magnesia bath, in order to expel the greater part of the excess of sulphuric acid. The pro- duct was then dissolved in a, small quantity of ice-cold water, the heavy metala (platinum, &c.) precipitated by hydrogen sulphide, and the excess of the latter expelled first, by the use of a water-pump, then by meam of a current of air. I n this way a solut.ion was obtained, from which, on adding three times its volume of absolute alcohol, the whole of the cerium was thrown down in the form of a fine crystalline powder or" the sdt Ce2(S0J3 + 8Hz0.After washing the salt with absolute alcohol, dehydrating at a geut1.e heat, and again precipitating with alcohol, a completely neutral cerous sulphate was obtained. Although free from any excess of sulphuric acid, the salt is not pure, even if it be thrown down from most carefully prepared purified alcohol, i t retains traces of foreign organic matter, probably betaine, and consequently turns yellow or brownish on subsequently heating. I t dissolves in water, also wiih a peculiar feeble empyreumatic odour. To p u ~ f y it, the salt must therefore be once more dissolved in cold water, and after filtering, the solution contained in a beaker is pliinged886 BRAUNER : CONTRIBUTIONS TO THE quickly into boiling water, so as to heat it to 100".If the hot super- saturated solution be now stirred with a glass rod, the salt present is instantly precipitated as a fine crystalline powder of the composi- tion Cez(SOa)3 + 6Hz0. This is collected with the aid of the pump on a platinum cone, and can be at once placed in a bottle, for it dries in a few instants when put on a smooth filter-paper, Originally I had intended to convert the hydrated snlphate by strong calcination into ceric oxide, and to calculate the atomic weight from the relation of the oxide to the hydrated salt, a method which has been used by Nilson and Pettersson (Bey., 13, 1441 and 1453) in determining the atomic weights of beryllium and scandium.Unfor- tunately all cerous sulphates either alter on exposure to the air, or, if they are stable, they seem to include the mother-liquor in small cavities, a property of salts first noticed by Sorby. On heating the neutral solution of the sulphate to 40-50", Marignac's (Zoc. cit.) hydrate, Ce2(S04)3 + 9Hz0, was never obtained, but instead of this, white turbid crystals of the salt with 8H20 always separated out. By spontaneous evaporation in the air at the ordinary temperature, the same salt was obtained in beautiful clear and glistening crystals instead of the salt CeL(S04)3 + 12H20. At loo", the salt with 6Hz0 alone is separated, but it quickly alters in the air. It is possible that the hydrates with 5H,O, 9Hz0, and 12Hz0, which I could not obtain from neutral solutions, crystallise only when free sulphuric acid is present.For these reasons, I was unable to prepare a, cerous sulphate with a definite (theoretical) amount of water of crystallieation which could be used for the atomic weight determination. In only two out of twenty cases in which the water was exactly determined was the theoretical amount of water found, viz., in the clear crystals, Ce2(SOJ3 + 8Hz0, obtained on spontaneous evaporation at the ordi- n a q temperature. As I had to give up the above plan, I tried to prepare the anhy- drous sulphate. It is impossible to obtain it by simply heating the hydrated salt in the air, for at a low temperature the water is not entirely given off, and at about 500" the salt may lose a trace of sulphuric acid, or it absorbs some oxygen and becomes heavier and slightly yellow-colonred by passing partly into ceric salt.But, on following Baubigny's (Compt. rend., 97, 854) example, I found that, at the temperature of boiling sulphur, cerous sulphate entirely loses its water without being decomposed or otherwise altered. Hitherto it has not been pery easy to operate with boiling sulphur, and yet I wanted an arrangement that would allow me to heat the salts for many weeks at 440" without special difficulty. After many trials I succeeded in devising an apparatus for this purpose. A veryCHEMISTRY OF THE CER’CTE METALS. 887 thin glass beaker, 18 cm. long and 7 cm. in diameter, is covered with a, sheet, of thick cardboard, having in its middle a round opening 4 cm.in diameter. To prevent this cardboard from burning, it is soaked repeatedly with alum, soluble glass, or sodium tungstate. Through the opening in the cardboard is passed a test-tube of thin glass, 20 cm. long and 4 cm. wide, the bottom of the tube being 4 cm. above the bottom of the beaker. The beaker is kept suspended in a wire triangle, and its bottom rests on a piece of thin wire gauze. The beaker is first placed on a sand-bath, and about 50 grams of sulphur are fused in it. Then it is placed on the gauze and heated with 2 or 3 Bunsen’s burners, so that the sulphur boils. In this way the whole of the beaker becomes filled with the vapour of boiling sulphur, which condenses on the sides, and flows down again. In order to prevent the upper portion of the beaker from being too strongly heated, the cardboard from carbonisng, and the sulphur-vapour from escaping, it is surrounded with a shorter open glass cylinder (a broad beaker with the bottom cut off) about 12 cm.high and 11 cm. wide, covered at the top by a plate of thin sheet copper (15 cm. square), having in its middle an opening of 7 cm., through which the thin long beaker (the sulphur-bath) passes, so that only its lower two-thirds are heated to the boiling point of sulphur, whilst the upper third, being freely exposed to the air, is prevented from becoming too strongly heated. With such an arrangement, the vapour of boiling sulphur reaches to two-thirds of the height of the bath, and the lower part of the test- tube is surrounded by it.When the cerous sulphate is to be dehydrated, it is placed on a small platinum crucible, and this is suspended by a loop of long thin platinum wire, the upper end of which is bent over the upper edge of t h e test-tube, in order to prevent the crucible from falling into the boiling sulphur, if the test-tube should crack. (Once, before I made this arrangement, the tube cracked, but, although the crucible wa,a plunged for a quarter of an hour in boiling sulphur, it was not altered in appearance or weight after being washed with potash solution.) The sulphur is then heated slowly to its boiling point, and after a while the platinum crucible is surrounded by sulphur-vapour far above its upper edge. Whilst the greater part of the water of crys- tallisation of the sulphate is escaping, the test-tube is kept open until a cold beaker held over no longer shows signs of dew.During the operation, the crucible is covered with a lid having the ear cut o f f , so that there is but very little space between the crucible and the side of the test-tube. When water-vapour ceases to escape, the test-tube is covered with a porcelain crucible lid, and the bath is heated until the weight of the crucible plus sulphate is found to be constant. This is easily effected if after one hour’s heating the salt be stirred with a888 BRAUNER; CONTRIBUTIONS TO THE thick platinum wire and heated for another hour. When the opera- tion is finished, the sulphur which has cooled down so that it no longer takes fire in the air, but is still fused, is poured out into a porcelain basin, for if it is allowed to remain in the beaker i t would certainly crack either as the sulphur cools or on fusing it again.When these precautions are observed, the same quantity of sulphur may be kept boiling in this simple apparatus for half a year or longer, from morning to night, without fear of anything happening t o it. When hydrated cerous sulphate is heated in the above apparatus until the weight is constant, and then allowed to cool in a small desiccator containing phosphorus pentoxide, it is found to be per- fectly anhydrous, without, however, undergoing the slightest decom- position ; the water which escapes from it, and which can be collected on a cool beaker, being neutral and unaffected by barium chloride.I f the anhydrous sulphate be heated to a higher temperature in 8 test-tube, no trace of water is given off, but a mixture of sulphur dioxide and trioxide escapes, so that the decomposition takes place in accordance with the equation Ce20,,3S0, = Ce204 -t 2S03 + SO,. This behaviour affords evidence of the powerful reducing power of cerous oxide, and it will be easily understood that it cannot be pre- pared in the free state. For analysis, the anhydrous sulphate was care- fully heated in a double platinum crucible over the flame of an ordinary burner, until sulphur trioxide fumes were no longer given off. In order to expel the last trace of sulphuric anhydride, I tried heating the salt to a white heat in a Fletcher’s blast furnace with injector, but I had to relinquish this plan, as not only does the cruciblelid becomes welded to the crucible, but the platinum seems to evaporate per- ceptibly at this high temperature; the inner of the two platinum crucibles which is not exposed to the direct flame, losing in a short time as much as 12 mgrms.I f the injector is put in a vertical position, and the air blown in in such a way that the flame, which is generally 30 to 50 cm. long, is converted into a short, hissing, hardly visible one (the flame will be often blown out entirely before the necessary practice is obtained in regulating the air and gas supply), a temperature is obtained in the free air at which an ordinary pretty thick platinum wire fuses instantly. This is certainly the highest temperature obtainable from a mixture of gas and air without a furnace, and I think that this simple arrangement will prove useful to chemists.The cerous sulphate contained in a double platinum crucible loses every trace of its sulphur at this temperature in 10 to 15 minutes, and it will take weeks before the inner crucible loses 0*0001 gram in weight.CHEMISTRY OF THE CERITE METALS. Weight of CeO,. 0 -7717 .7g58 1.03534 1‘1308 889 Loss of Per cent. of (‘Atomic weight.” weight. CeO,. Ce = 0 -5033 o . 5195 ::: z:! :$ :;:} Mean. . 139 -78 0 %7771 60.440 139 ’53 Mean,, 139 .49 0 -7394 60 -44 139 -46) ---------- ----------- Experiments with Mixt uws. Before the above method of operating with boiling sulphur had been worked out, I tried to decide whether the above precipitate Na could be split up into different fractions.For this purpose, one part of it was converted into the neutral sulphate, which was dissolved in water, and then fractionally precipitated with dilute ammonia. I will call the most basic portion remaining in solution A. The precipitate was dissolved in dilube sulphuric acid, and again precipitated. After four precipitations, the least basic portion B was obtained. On heating the hydrated neutral sulphate prepared from the portions A and B high over the flame in a double platinum crucible t o constant weight, Wolf’s “ anhydrous ” sulphate (it is really n o t anhydrous) was obtained, and this was converted into ceric oxide by strong calci- nation. The formulze used for the atomic weight calculation will be given later on. The following results were obtained :- Weight of Ce? (S 0,) 3.These numbers are not absolutely exact, as the water was not entirely expelled, but they may be considered relatively true, for they were determined by the same method. As the “ atomic weight ” was in one case Ce = 139.78, and in the other Ce = 139.49, the question remained open whether the material used was homogeneous. This circumstance suggested an attempt to split up a portion of the precipitate N,, which WAS less pure, but contained only traces of didymium. The basic ceric nitrate from this was converted into cerous sulphate, from which the excess of free acid was removed by alcohol. The aqueous solution of the sulphate was partially precipi- tated by adding to it strong alcohol, drop by drop, and in this way the portions A, B, C, D were obtained.These precipitated sulphates were dried between smooth blotting-paper, and then in a state of fine powder dehydrated in the sulphur-bath and analysed as before, witch the following results :-890 BRAUNER : CONTR1BI;TIONS TO THE Per cent. of “Atomic CeO,. weight .” 60 *591 140 - 34 60 -568 140 -18 60 -545 140 90 i 60.906 142 *65 I ----- Weight of Weight of Loss of Ce,(SdA. I CeO,. 1 weight. A.. . . 1.3601 B . . . . 2.4780 C . , .. 2.3191 D.... 1’5179 0.8241 0 *5360 1 * 5 0 N 0 -9771 1.4041 0 -9150 0’9245 0 -5934 The difference in the percentage of ceric oxide of the single frac- tions is far more striking than in the first case. The oxide obtaiued from fraction D had a peculiar flesh colour mixed with a pale orange, and it is very remarkable that it turned grey under the influence of light, whereas pure ceric oxide is white with a yellowish tint, and does not alter when exposed to light. The portions A, €3, and C were far less orange than I).I f we assume that the loss of weight on ignition is represented by the same equation as in the case of pure cerous sulphate, viz., Ce203,3S03- (3S03-0) = 2Ce02, the “ atomic weight ” of the earth metal in the fraction D would be R = 142.65. It will be seen from the numbers given hereafter, that the numbers found for A, B, and C represent very nearly the true atomic weight of cerium. The high percentage of oxide in fraction D cannot be due to the presence of didymiurn, because anhydrous sulphate of didymium contains only 58.09 per cent. of the oxide, and the per- oxide would be completely decomposed at such a high temperature.Still, it might be due to the pretience of thorium, its anhydrous sul- phate containing 62.42 per cent. of the earth. In order to entirely exclude any thorium possibly pyesent, the following process was used. The earths contained in the filtrates F1, F,, F,, and F4 were preci- pitated with potassium hydroxide, and the precipitate, consisting chiefly of cerons hydroxide, was suspended in strong caustic potash solution, and treated for three days with chlorine, in order to remove the greater part of the lanthanum and didymium present. After thoroughly washing, the precipitated ceric hydroxide was dissolved in nit.ric oxide, and the excess of acid removed by evaporation, when a gelatinous mass of ceric nitrate was obtained, Its Rolution in cold water was poured into boiling water, and so the greater part of the purer cerium salt was thrown down a8 basic nitrate. From the filtrake containing impure cerium salt, the earths were thrown down with ammonia and converted into the sulphates.After dissolving in five parts of ice-cold water and separating the heavy metals with hydrogen sulphide, the solution was heated at 60-70” for some time. At this temperature most of the cerous sulphate separates out, and if any thorium be present, its sulphate will, according to Nilson’s experiments (Bey., 15, SSlU), also crystallise out. The same holdsCKEMISTRY OF THE CERITE METALS. 891 Loss of weight. good as regards lanthanum sulphate. The last mother-liquor contains, besides cerium, some didymium.It was split up into two parts by addiug strong alcohol, and the Zast precipitate (Le., the most soluble salt) was recrystallised from water and used for the atomic weight determination :- Per cent. of R02. ROz. 0 '7190 0 -9299 0 -3034 1 -8649 2 -4310 0 -7863 61 *M 61 *135 61 -414 Mean.. . . 61 '331 ---- 1 -1459 1'5011 0 *dl829 I I I This strikingly high percenta,ge of oxide, if calculated out i n accordance with the above equation, would correspond with an *' atomic weight " of R1ii-'v = 145-72. The material wa5 not entirely free from didymium, and, although it was improbable, for the reasons stated, that its presence could render the percentage of the oxide higher, experiments were under- taken with cerous -sulphate artificially contaminated with a didymium salt, in order to decide the question.The following tive results were obtained :- Sulphate. Oxide. Per cent. of oxide. 0.6941 0.4203 60-55 1,6320 0.9878 60.33 little nega- I could not yet decide the question as to whether the presence of one of the many rare earths, some of which have been but very little studied up to this time, makes the atomic weight of impure cerium higher, neither could I find out the reason of the high numbers obtained. In any case, it is seen from the above experiments, that under certain conditions " cerium '' may consist of a mixture. The nature of this admixture must be ascertained by further experiments ; but before this is done we must become acquainted with the pro- perties of really pure cerium.Experiments with Pure Material. The object of the following series of experiments was to ascertain how far cerium has to be purified in order to furnish a truly homo- geneous product. For the experiments, the following of the above- mentioned precipitates of basic nitrate and the corresponding filtrates were used :-892 2 -2670 2 -1869 2 *5807 2 *0149 1 * 6519 1 -6193 ---- --I_-- ---- BRAUNER: CONTRLBUTIONS TO THE 1,3749 1 *3252 1 -5648 1.2216 1 -0013 0 -9815 NS NB N, N8 Ng NIO NIL FS E', F+J F8 Fg FIO FII. These were found to be entirely free from lanthanum and didymium. It will be seen from an inspection of this series, and a considera- tion of the process of fractionation, that the cerium in the Jiltrates is far more strongly " fractionated " than the precipitates, especially as the quantity of earth in each filtrate is much smaller than that in the corresponding precipitate. For this reason the filtrates alone were used to determine the question of homogeneity, and, as no funda- mental stoechiometric numbers were to be obtained, the following simple process was used for the preparation of cerous sulphate from them:-The filtrates, after adding to them some of the sulphuric acid, and later on some sulphurous acid, were evaporated to dryness in a platinum basin, and from the sulphates obtained in this way the excess of snlphuric acid was driven of€ by heating the residue in a magnesia-bath; it was then dissolved in water, and the sulphate thrown down by alcohol.After repeating this process, the anhydrous sulphate was dissolved in water, and the neutral aulphate separated out by heating the solution at 100".The dehydration in the sulphur- bath and the analysis were carried on in the way described above. The results are given in uncorrected numbers :- I--- I --- 2 *3797 1 -4.424 { 1 1.8258 1 1.1073 .............. Fs F6 + F, .......... The two together.. .. F8 + F g . .......... The two together.. .. F1, + F11 .......... The two together.. .. Per cent. of Ce02. 60.614 60 *648 60 *649 (maximum). 60 -597 (minimum). 60.634 60 -627 ----- 60 -615 60 -612 Mean.. .. 60 -624 The material used for these experiments, although containing no other earth metal .but cerium, had been too much in contact with filter-paper, with glass and porcelain vessels in strongly acid solution, and with air, so that the nunibers were neither corrected, nor were they used for the calculations of the atomic weight.But, as they are for all fractions exactly the mme, showing neither a regular increase nor decrease, and differ from the mean number at the out- side by * 0.025 of a unit in percentage, the conclusion must be drawnCHEMISTRY OF THE CERITE METALS. 893 that the cerium of the filtrates F6 to FI1 is a perfectly homogeneous body. Now it remained only to use the last of all the precipitates, viz., Nil, containing the best purified cerium, for the deJinite atomic weight determination, and to ascertain whether, on comparing it with the filtrates mentioned above, it furnishes the same results. E'or the same purpose, in I and I1 (see table), part of the precipitate N1, was used.The remaining 21 determinations were made with a material obtained from difeyent preparations, in order t o meet, the objection that only one kind of material had been used. For, in such a case, even if the results agreed, they might not be accurate. It is almost unnecessary to remark that the following series of determinations was made with the greatest possible care, and that they involve the correction both of weights and for displaced air. I did not exclude one single experi- ment which I made, not even numbers XIV and XXIIT, although they may be considered a little too low, for the difference of weight to which these low numbers are due, falls within the allowed experi- mental errors. Number of experiment. I.. 11.. 111.. IV.. V..TI.. VII.. VIII.. IX.. X . XI.. XII.. XIII.. XIV.. xv.. XVI.. XVII.. XVIIT., XIX.. xx.. XXI.. XXII.. XXIII.. Total.. . . --- -- -- Cerous sulphate. 2 - 16769 2.43030 2 * 07820 2.21206 1.28448 1.95540 2 * 46486 2 *04181 2.17714 2 -09138 2.21401 2 * 44947 2.22977 2 * 73662 2-62614 1 -67544 1 a 57655 2 * 72882 2 10455 2 * 10735 2 * 43 557 3.01369 4.97694 53.77424 -- --- Ceric oxide. --- 1 * 31296 1 * 47205 1 a 25860 1 *33989 0.77845 1 * 18436 1 - 49290 1'23733 1'31878 1 -26654 1 * 34139 1 * 48367 1 '35073 1 *65699 1 59050 1 - 0 1470 0'95540 1'65266 1 * 27476 1-27698 1-47517 1.82524 3 -01372 32 -57367 Loss by calcination. --- 0.85473 0-95825 0'81960 0.87217 0 - 50603 0.77104 0 * 97196 0 * 80448 0.85836 0 82484 0.87262 0.96580 0.87904 1.07963 1'03564 0 a 66074 0 * 62115 1 * 07626 0.88979 0.83037 0 * 96040 1.96322 21.20057 1 * 18845 -~ Percentage of CeOz.60.5695 60.5707 60.5620 60-5721 60 * 6043 60.5687 60 * 5673 60.5997 60.5739 60.5600 60 5863 60.5'71 1 60-5771 60 -5488 60 -5642 60- 5632 60.6007 60.5600 60.5716 60 * 5965 60- 5678 60 * 5649 60.5537 -- 60.5747 Atomic weight of cerium. 140 - 183 140.191 140 * 128 140-201 140.176 140- 167 140.400 140.215 140' 11 4 140 * 304 140.194 140.237 140.033 (min.) 140 * la 140.137 14Q * 407 140.110 140 * 198 140.377 140 * 170 140*150 14Q * 068 140.433 (mx.) 140 * 2210 For the calculation of the atomic weight Lothnr Meyer's and Seubert's example was followed, viz., the several amounts of sub-894 BRAUNER : CONTRIBUTIONS TO THE stance weighed were added together, and the atomic weight calculated from the totals according to the following formula.(It has been proved mathematically by Ostwald, that such a method of calculation is correct.) Ce2(S04), : 2Ce02 = 53+77424 : 32.57367 grams, when if Cer(SO& = 100, CeOz = 60.5747. grams. Difference of Ce2(S04), and Ce02 (loss of weight) = 21.20057 32.57367 x (3303-0) 2CeO2-40 = Ce. 2 = 2Ce02, I€ we replace all by numbers and take for 0 = 16 and S = 32.06, 2 1.2005 7-- we have (3S03 - 0) = 22418; then we have- 32.57367 x 224.18 = 344.4$20 2Ce = 280.44'JO Ce = 140.2210. 64 21.2005 7 'If calcuIated with hydrogen numbers, 0 = 15.96 and S = 31.98, then- Ce = 139.8707. I have not calculated the atomic weight and its probable error by the method of least squares, because the following different numbers have been Calculated by different chemists (for 0 = 16) as the atomic weight of suIphur on which such a calculation &ould be founded.Stas ........................ 32.074 Ostwald .................... 32.0626 Sebelien" .................. 32.0608 L. Meyerand Seubert ........ 32.0592 Clarke.. .................... 32.058 The extreme difference of these numbers is = 0,016, and the calcu- lation of the probable error would become uncertain. It is, no doubt, a very good principle to determine the atomic weight of an element by several independent methods ; unfortunately i t was impossible in the above case from want of choice of suitable cerium compounds. I have tried to obviate this objection by making a greater number of determinations. On the other hand, my number is severely controlled by the numbers f Sebelien, Beitvage zur Geschichte der Atomgewichte, Braunschweig, 1884, p.155.CHEMISTRY OF THE CERITE METALS. 895 found by Robinson (Zoc. cit.) foy both numbers, determined by widely different methods, are in as good an accordance as can be expected :- For 0 = 16 Ce = 140,2593 140.2210 For 0 = 15.96 Ce = 139.9035 139.8707. Robineon. Brauner. If we compare the above series of determinations with that made for the purpose of investigating the homogeneous nature of cerium (from the filtrates I?, to F,,), both series are seen to agree well, and from this the conclusion must be drawn that the’ pure cerium pre- parations used by me were homogeneous. The simple method which I adopted for the purification of cerium preparations must be considered very good, as from 1380 grams of crude oxides, containing in all 690 grams of ceric oxide, I obtained 720 grams of pure nitrate, representing over 500 grams of ceric oxide.Discussion of Former Determkations of the Atomic Weight of Cerium. It will be almost unnecessary to discuss several of the above quoted determinations, for they were carried out with a material containing other cerite metals. This may be said of the experiments made by Hisinger in 181616, by Beringer in 1842, and by Rammelsberg in the same year. The method followed by Hermann (1843) and by Marignac (1848), vie., precipitation of the suIphuric acid in a solution of cerous sulphate with barium chloride, has been declared by Marignac himself to involve a considerable source of error, as the barium sulphate carries down some cerium with it.Besides, for the reasons given by Buhrig, and quoted above, it is very improbable that the sulphate used by these and other authors (especially by Jegel) had a definite normal composition. Jegel (in 1858) and Rammelsherg (in 1859) determined the atomic weight of cerium by the combustion of cerous oxalate. It has been shown by Nilson (Ber., 15, 2519) in his paper on the atomic weight of thorium, that the method of elementary analysis of an oxalate involves several errors which make it unsuitable for the exact determination of the atomic weight of an element. I shall therefore not enter more fully into an analysis of the papers published up to 1860, but proceed to discuss the work done by Wolf.As regards, first of all, his observation that the atomic weight of cerium diminishes on further purification of the preparations, I think it may be regarded as conJirmed by my own experiments. But this decrease ceases as soon as we get to the precipitate N, (it would cor- respond to Wolf’s NE which, however, he never obtained). Wolf’s ceric oxide was white. The same was the case with my purest ceric oxide, though I should prefer to call it. the palest ‘‘ chamois.”$96 BRAUNER : CONTRIBTJTIOSS TO THE On the other hand, I cannot confirm the very low atomic weight found by Wolf. Firstly, Wolf did not prove that his sulphate bad a definite normal composition. His hydrated salt, as can be concluded from my own experiments on this subject, most probably did not con- tain the theoretical amount of water of crystallisation, and according to Buhrig it must have contained some free sulphuric acid, which can be got rid off only by the process quoted above.I f these two sources of error are not taken into consideration, the atomic weight of cerium will be found lower than it really is. As regards the numbers calculated from the “ anhydrous ” sulphate, they cannot be regarded as exact, for cerous sulphate, heated high over a small flame in a doable plabinum crucible, retains a trace of water, as has been already pointed out by Buhrig, and as may be seen from the following experiment. 3.0283 grams of crystallised cerous sulphate gave, on heating for two hours in a double platinum crucible at a temperature at which the bottom of the outer crucible was red hot for a short time (the tem- perature applied by Wolf was never so high), 2.3343 grams of “an- hydrous ” salt. On heating it in the sulphur-bath at 440°, it lost the last trace of its water, and its weight diminished by 0.0046 gram, namely to 2.3797 grams.As at a high temperature the sulphate yielded 1*4424 gram of Ce02, the atomic weight, calculated from the first number, would be Ce = 139.65 instead of Ce = 140.22. Secondly, I found that, on precipitating a solution of cerous sulphate with boiling oxalic acid solution, a trace of cerium, the oxalate of which is partly soluble in the free sulphuric and oxalic acids, remains in solution even after long standing. 1.3506 gram of anhydrous sulphate, precipitated and ignited by Wolf’s method, gave 0.8173 gram CeOa = 60.314 per cent.Directly analysed, tlhe same sulphate gave 60.60 per cent. of CeO,. This error, although slight, gives a smaller atomic weight. Thirdly, on precipitating the filtrate from the cerous oxalate with barium chloride, a, little more barium sulphate is always obtained than corresponds with the sulphuric acid contained in it, for not only is the trace of cerium which remains in solution carried down with barium sulphate, but also some barium oxalate. This causes the atomic weight of cerium found to be lower. From the above filtrate, after separation of cerous oxalate, 1.6831 gram of BaS04, corresponding with 0.5781 gram, or 42.803 per cent. of SO3, was obtained (theory requires only 42.24 percent). From the relation of 0.8173 CeOz : 0.5781 SO3, the atomic weight calculated is Ce = 137.78 instead of Ce = 140.22. If only one or all of these sources of error are left out of considera- tion, t 7 ~ e atomic weight of cerium found will always be lower than theCHEMISTRY OF THE CERITE METALS. 897 true one. I think, therefore, that I have sufficiently explained +he low numbers found by Wolf. In striking contrast with Wolf’s work is that done by Biihrig, who found the high number Ce = 141.5. Biihrig analysed large quanti- ties of cerous oxalate by combustion (the details,will be found in Clarke’s recalcnlafion), but he made the mistJake of using a material resulting from one preparation only. I do not believe, however, that Buhrig’s oxalate contained an admixture of basic salt: as is sometimes stated. Another cause of error in Biihrig’s work must be looked for in the fact, as Nilson has shown (Zoc. cit.), that the analysis of oxalates by combustion is subject to constant errors which make the atomic weight higher. For example, Cleve, by this method, found the atomic weight of thorium to be Th = 23390 to 233.97, whereas Nilson’s analysis of the sulphate gave Th = 232.40. But, as Buhrig used for combustion large quantities of oxalate- about 10 grams at once-the loss of carbonic anhydride and theplus of water cannot have been the only source of the difference between t’he number obtained and the true one. I am inclined to believe that the reason of Buhrig’s higher number was partly the same which caused me to find the ‘‘ atomic weight” of the impure cerium to be R = 142.65, and even R = 145.72, for Biihrig points out distinctly that his oxide was yellow. Further, as this oxide when strongly heated is converted with loss of weight into one which is of a pale salmon colour, the former may have contained some of the unstable peroxide, t’he admixture of which would cause the atomic weight found to be a little higher. In conclusion, it may be pointed out that, in consequence of the present new determinations, the differences between the atomic weights of lanthanum, cerium, and didymium, elements following each other in the periodic system, harmonise far more than was pre- viously the case. Thus we have, La. Ce. Di. L---L~-~-J 138.2 140.2 142.3 Difference.. . . 2.0 2.1 VOL. XLVI1.

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DOI:10.1039/CT8854700879

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年代:1885

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898 LXXX1.-A New Method of Preparing Aromatic Hydrocarbons. By R~CHARD ANSCH~~TZ. IN the course of a research on fumaric acid and malei'c acid, Wirtz and I noticed that a hydrocarbon was formed when phenylic fumnrate was distilled. This hydrocarbon was found to be stilbene, and its formation may be accounted for on the supposition that the phenylic fumarate loses 2 mols. of carbon dioxide. Phenylic cinnamate must be considered to be the first product of the reaction, and this in its turn gives off carbon dioxide, becoming stilbene, as represented by the following equations :- CH*COOC6H, CH.COOC,$& cx'co Oc6H5 CHsC6H5 I. II - co, = 11 Led by this consideration, I submitted several aromatic cinnamic ethereal salts, prepared by Mr. Selden a t my suggestion, to slow dis- tillation under ordinary pressure.I n each case, I noticed that there was an evolution of carbon dioxide during the distillation, and that afterwards products of decomposition distilled over. All the cinnamic ethereal salts were prepared by heat.ing the phenol with pure cinnamic chloride (b. p. 140" under about 16 mm.). Phenylic cimamate, C6H5.CH : CH*COOC6H5, melts a t 72.5" ; it is readily soluble in alcohol, and boils under a pressure of 15 mm. a t 205-207" without decomposition. The hydrocarbon obtained from it by slow distillation under ordinary pressure proved to be stilbene : it fused a t 1 2 4 O , and when treated with bromine gave stilbene bromide, sparingly soluble in alcohol and chlor.oform, and melting at 235". Paracresylic cimsamate, CsH,*CH : CH.COOC6H4*CH3 [COO : CH, = 1 : 41, melts at 100-101"; it is more sparingly soluble in alcohol than the phenylic salt, and under 15 mm.pressure boils at 230" without decomposition. On slow distillation under ordinary pressure, it yields methylstilbene, a substance very similar to stilbene ; this crystallises from alcohol in plates which melt at 120", and exhibit a beautiful blue fluorescence. When treated with bromine in a solu- tion of chloroform, methylstilbene gives a bromide readily soluble in ctiloroform, but only very sparingly soluble even in boiling alcohol ; after being reciytnllised from alcohol, it melts to a brown liquid,ANSCHUTZ AXD WIRTZ : AROXATIC ETHEREAL SALTS. 8'39 The decomposition of the two ethereal salts in question on slow distillation under ordinary pressure chiefly takes place, therefore, in accordance with the eqnations- CsR,*CH : cH-cooc,H5 = C,H,*CH CH*C,H, + CO,; CaH,.CH : CH*COOC,H,*CH3 = CJ&.CH CH-CGHk.CH3 + CO,.Thymy tic ciitnarnute, C,H,*CH: CH*COOC,H3(C3H7)*CH3 [COO : C3H7 : CH, = 1 : 2 : 41, melts a t 69-70", and under about 15 mm. pressure distils at 239- 240' without decomposition. On heating it under ordinary pressure, carbon dioxide is given off, but the liquid substances obtained from it have not yet been studied. P-Napkthy Zic cinnamate, C6H5*CH CH*COOCloH7, melt's a t 101- 102", and gives, on distillation under ordinary pressure, a large quantity of hydrocarbon, sparingly soluble in alcohol ; when recrystal- lised from alcohol, this forms glistening plates which melt at 14.5", and are readily solublt, in chloroform. The bromide is readily soluble in chloroform, and can be recrystallised from boiling alcohol, in which it is very sparingly soluble ; it melts a t 192", becoming black. Pheny Zic succinate which, according to Weselsky, boils undecom- posed a t 320°, may be completely decomposed by slow heating, carbon dioxide being evolved. Amongst the products of decomposition, di- benzyl is only found in very small quantity ; lower boiling substances smelling of phenol are chiefly produced, but these have not yet been studied. As it is evident that the reaction described may be generalised, the study of the conditions under which carbon dioxide is split off from ethereal salts of carboxylic acids has been commenced in the Bonn Laboratory.

ISSN:0368-1645    

DOI:10.1039/CT8854700898

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年代:1885

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A4NSCHcTZ AYD WIRTZ : AROMATIC ETHEREAL SALTS. 899 LXXXI1.-On the Deconzposition n$ Aromatic Ethereal Salts of Furna ric A d d . By RICHARD ANSCH~TZ and QU~RIN WIRTZ. WE have for some time been occupied with the study of the action of phosphorus pentachloride on maleic anhydride. W. H. Perkin (Bet-., 14, 2548), who has examined this reaction, states that on distilling malei'c anhydride with phosphorus pentachloride, as might have been expected, furnaric chloride is produced. The reaction, however, is not a complete one, and a great part of the unaltered anliydride passes over towards the end of the operation. We have900 ANSCHUTZ AND WIKTZ : AROMATIC ETHEREAL SALTS, worked in such a manner that after the reaction was completed, we distilled the products under diminished pressure, and after repeated fractional distillation, we succeeded in isolating a liquid boiling at 70-71" under about 11 mm.pressure ; this on analysis gave numbers which are in accordance with the formula of male'ic chloride. We observed that fumaric chloridc boils under 14 mm. pressure a t 60". Circumstances compelled us t o discontinue the experiments for three mont>hs, and during this time the product of the action of phos- phorus pentachloride on malejic acid anhydride remained untouched, sealed in a glass tube. On continuing the research we subjected the liquid which previously boiled a t 70-71" under 14 mm. pressure again to rectification under diminished pressure. The chloride now begzn to boil a t 60" under 14 mm. pressure, the temperature rising to 75" towards the conclusion of the distillation, so that the chloride had evidently changed its natuye, As one of us had formerly (Ber., 12, 2281) observed that male'ic acid is completely changed by acetyl chloride into its anhydride, and that malei'c acid is not converted to fumaric acid by dry hydrogen chloride, it seemed possible that two different ethereal salts would be produced if fumaric chloride and the product of the reaction of phosphorus pentachloride on male'ic acid were treated with a dry alcohol.By the hydrolysis of the ethereal salts prepared from the product of the reaction of phosphorus pentachloride on male'ic acid anhydride we might obtain the desired information as to the nature of the chloride produced. This consideration induced us, in the first place, to pre- pare phenylic fumarate from fumaric chloride a.nd phenol, because-of the more easily obtainable alcohols--phenol is the most readily secured free from water.CH*C 00 C6H5 CH.COOC,H, Phenylic furnarnte, 11 , crystallises from alcohol in white needles melting a t 161-162", very sparingly soluble even in hot alco- hol. If rapidly distilled, it passes eve+ partly unchanged, but is partly decomposed into carbon dioxide and stilbene. If phenylic fumarate is heated very slowly, it is almost wholly decomposed in this manner, an oil of aromatic odour, which we have not yet studied, accompanying the stilbene. The explanation of this reaction, which is given in the preceding communication, involves the intermediate formation of p henglic cin- namate ; the correctness of our explanation woiild be placed beyond doubt if we could succeed in finding this compound among the products of the decomposition.We therefore tried to conduct the reaction step by step, and ceased heating the phenylic fumarate asANSCHUTZ AND WIRTZ : AROMATIC ETHEREAL SALTS. 901 soon as half the quantity of carbon dioxide formerly observed had been expelled. The residue in the fractionating flask was distilled under diminished pressure, and the solid distillate recrystallised from alcohol. The greater part of it consisted of stilbene, but we suc- ceeded without difficulty in isolating phewylic cinnamate from the alcoholic mother-liquor ; this on Oreatment with an alcoholic soh- tion of potash, gave pure cinnamic acid. C H* C 0 0 C,H, Paracresydic fimarate, 11 , is verj sparingly soluble in CH*COOC6H5 alcohol, and melts at 162" ; it is decomposed when heated, losing carbon dioxide and yielding two crystalline substances, one of which is sparingly, the other easily soluble in alcohol.The former is dimethyl- stilbene melting at 179'. It gives a bromide, easily soluble in chloro- form and very sparingly soluble in alcohol, melting with decom- position at 203-204". The soluble substance melts at 79" and crystallises in glistening scales ; it is perhaps phenylic methyl- cinnamate. From these results it follows that hydrocarbons belonging to the stilbene group may be prepared from the fumaric and cinnamic acid ethers of the monohydric phenols, and of course the ethers of cin- namic acid, with the exception of the phenyl ether, give hydro- carbons with different aromatic radicles-that is, " mixed stilbenes ; '' whilst the fumaric acid ethers gire hydrocarbons with the same aromatic radicles, that is, " symmetric stilbenes." Moreover, the fixmaric ethers of the phenols give phenyl ethers of acids belonging to the cinnamic acid group. The formation of stilbeiie from phenyl fumarate is of special interest also, from the hydrobenzoins being brought into near relation with fumaric acid by this transition, although in an indirect manner. We shall endeavour to prepme the acetyl ethers of the Eydrobenzoins from the phenyl ethers of the acet8yltartaric acids by elimination of carbon dioxide. VOL. XLTIL.

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DOI:10.1039/CT8854700899

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年代:1885

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902 LXXXIII.--The Influence of Silicon o n the Properties of Cast Iron. Part 11. By THOMAS TURNER, Assoc. R.S.M. (Demonstrator of Chemistry,. Mason College, Birmingham). THE present paper is a continuation of one recently published (this vol., p. 577) in which an account was given of a series of experiments intended to determine the influence of the regulated and gradual addition of silicon to cast iron of more than usual purity. A descrip- tion has already been given of the general method of procedure, the composition of the materials used, and the analyses of the metal obtained. Experiments were also described by which the influence upon tensile strength and modulus of elasticity was gradually made clear, and the effect upon the proportion of graphitic carbon shown. A further account, though necessarily incomplete, was also given of the appear- ance on fracture, the relative fluidity of the melted material, the appearance of the castings, soundness of metal, and resistance to fracture.Other experiments ha.ve now to be mentioned i n connection with the influence of silicon on the physical and mechanical properties of cast iron. 8pec;fc Gravity .-The specific gravity of the specimens might obviously be determined in two ways: on the one hand by the employment of fragments such as borings or turnings, or on the other by the use of pieces of considerable size. It appeared at first doubt- ful which of these two methods was to be preferred. It had been already shown that the 10 specimens to be operated upon varied very much in tenacity and hardness, and it therefore appeared probable that their density would be unequally affected by the different forces exerted upon them while being reduced to small fragments.On the other hand, the presence of any unsoundness in the specimen would have a much greater influence upon the result if large masses were employed. Under these circumstances, it was considered best to determine the specific gravity both in a turned piece of considerable size, and in the turnings from the specimen. For the determination of the specific gravity in mass, it was con- sidered best to employ large pieces all as nearly as possible of one size. For this purpose, cylinders 3 inches long and 1 inch in diameter were prepared, each weighing upwards of 270 grams, whilst their maxmium difference of water displacement did not vary more than - + 0.06 gram, except in one instance, where the specimen afterwards proved to be unsound.The pieces were washed with alcohol to freeTURNER: INFLUENCE OF SlLICON ON CAST IRON. 903 them from any accidental grease, and suspended by a fine platinum wire in water at 20". The turnings produced during the preparation of the cylinder3 were used for the determination of the specific gravity of fragments. To avoid any mistake, the specimens were served out singly to the workman, and the operation personally superintended throughout, each cylinder being mazked, rand the turnings labelled, before another specimen was commenced. In the determination itself, a modified Sprengel tube (Nicol, Phil. Mag., June, 1885, 455) was employed, by which considerable weights of metal could be operated upon, 17.5 grams being the least quantity employed.The tubes were filled with pamffi oil, of sp. gr. 0.79215, and immersed in a Nicol's (Phil. &lag., May, 1883, 339) constant temperature bath. In each case where much difference existed between the specific gravity of the cylinder and that of the turnings, duplicate experiments were made, and m these always agreed well together, it is probable that very tolerable accuracy was obtained. The results are given in the following table :- TABLE C.--Xpec$c Gravity of Cast Iron at 20" C. (Water at 20" = 1.) Silicon per cent. 0.19 0.45 0.96 1-96 2-31 2.96 392 4.75 7.37 9-80 Sp. gr. of cylinders. 7.560 7.510 7.641 7.518 7.422 7.258 7.183 7-167 7.128 6.9 7s Sp.gr. of turnings. 7.719 7.670 7.630 7.350 7.388 7.279 7.218 7.1 70 7.133 6.924 It will be noticed that there is not generally a very marked diifer- ence between the values obtained by the different methods. The turnings from the three strongest specimens, however, show a diminished density (compare this vol., p. 580), and this is particularly marked in the middle one of the ihree, containing 1-96 per cent. Si, which possesses the highest tenacity of the series. On the other hand, the rest of the turnings, with the exception of silicon pig itself, show an incyeased density due to the mechanical force exerted during turning. In the case of the cylinder containing 0.45 per cent. Si, the specimen was afterwards proved to be faulty in the interior, and this evidently accounts for its irregularity.3 R 2904 TURNER: THE INFLUENCE OF SILICON FIG. 8.-sPECIFIC GRAIYTY. In Fig. 3 these facts me expressed graphically, the curve being continued, on a, reduced scale, with data, obtsined from TTatfs’ Dictio?za?*y, 1st Suppl., p. 753, where an account is given of some silicides of iron prepared by Hahn. Relative Hwd?zess.-The smooth ends of the cylinders employed in specific grarit,y experiments were used for the determination of rela- tive hardness. It had been originally intended to do this by means of sb weighted steel point, but, on the advice of Dr. Nicol, a cutting diamond was substituted for the steel point. The diamond was firnily fixed, vertically, point downwards, into t’he end of a long lath, and a t right angles to its length.The lath was then balanced in the middle, mid fixed so as to allow of free motion in a horizontal plane. The smooth end of the cylinder to be operated upon was brought under- neath the diamond, and weights added until a perceptible scratch was produced on drawing the diamond across the surface of the metal. A note was made of the weight which had been added, and this was gradually diminished until no visible scratch was produced on again drawing the diamond over the metallic surface. The difference between the two observatioizs was generally 5 grams, and, on repeat- ing the observation upon the same specimen, the results obtained did not yary from each othei. by more than the same amount. I n observations of this kind, it was not considered necessary to use weiylits smaller than a gram.The i n e m of the two obscrvations was taken as the point desired,ON THE PROPERTIES OF CAST ZRON. 905 and the results obtained are given in Table D (below). It will be noticed that pure cast iron is the hardest of the whole series, and that the hardness is diminished by the addition of silicon up to 2 per cent. There is then no appreciable difference until 3 per cent. has been added, after which the metal is gradually rendered harder by con- tinued addition of silicon. TABLE D.-Relative Hardness. Silicon per cent. 0.19 0.45 0.96 1.96 2.51 2-96 3.92 4.75 7.37 9.80 Weight in grams. 72 52 42 22 22 22 27 32 42 57 These results may be graphically represented in a curve, as we have in Fig. 4, when it will be seen that the change produced is gradual and quite regular.Silicon per cent. Worlhzg QziaZities.-During the preparation of the cylinders pre-906 TURNER: THE INFLUENCE OF SILICON viously mentioned, especial notice was taken of the working qualities of the iron. The observations were made by an experienced workman, and they agree very nearly with the determinations of hardness given above. 0 per cent. Si. Very hard indeed ; rather unsound under the skin, but turned bright. 0.5 per cent. Si. Very hard, though not so hard as the previous specimen; there were several blowholes under the skin, and the specimen proved unsound when tested afterwards. Hard, though softer than the last specimen ; cut well, gave bright surface, and was quite sound. Good, sound, ordinary, soft cutting iron, of excellent quality ; turned surface darker in colour.Rather harder than the last, but otherwise the same. 1 per cent. Si. 2 per cent. Si. 2.5 per cent. Xi. 3 per cent. Si. 4 per cent. Si. 5 per cent. Si. 1.5 per cent. Si. 10 per cent. Si. The appearance of the turnings is also characteristic. Like 2 per cent. Like the latter, but rather harder. Cuts rather harder than 4 per cent., though not unusually hard. Still harder, andcuts very like the next specimen. The turned surface is not so smooth. Hard cutting iron, though still much softer than the first specimen (0 per cent.). These, at either end of the series, are small and of irregular shape, gradually passing into the longer curly turnings of good cutting iron as they approach the 2-3 per cent.specimens. Cruslting Strercgth,.-For the determination of the crushing strength, it was originally intended to employ the cylinders 3 inches long by 1 inch diameter, which had been used in the specific gravity experi- ments. But as the specimens mere of unusual strength, it was found necessary to reduce the diameter to 0.75 inch. The specimens were tested by Professor A. B. W. Kennedy, at University College, and I have again to express my obligation to him for the kindly interest he has manifested in these experiments. The results obtained are given in Table E (p. 907). The exact composition of each specimen has already been given (this vol., p. 581).ON THE PROPERTIES OF CAST IRON. 907 TABLE E.-Crushing Strength. (Tests by Professor Kennedy.) Silicon per cent.0 0.3 1 2 2.5 3 4 5 7.5 10 Breaking load per square inch. 7-7 Pounds. Tons. 168,700 75.30 204,800 91-42 w { ;;,"w& 60.53 62.05 172,900 77.18 207,300 9254 128,700 57.45 106,900 47-74 1 1 1,000 49-55 103,400 46.16 76,380 34.10 These figures illustrate the same fact, before shown in severalways, that on addition of small quantities of silicon the metal improves in quality, but gradually becomes inferior on the addition of larger per- centages. This is shown graphically by the curve given in Fig. 5 (p. 908), and for comparison the curves of tensile stren@h and modulus of elasticity hare been drawn to suitable scales, and are given in the same diagram. All three curves show the same gewal characters, though it will be noticed that the maximum point is dif- ferent in each case ; this difference, however, is not very considedle. It; will be observed that only six of the experimental resulk, or fwo-thirds of the whole, agree well with the curve drawn.B& it must be remembered that this class of mechanical tests is more liable fo v h t i c m than most others, errors of 5 per cent. not being uncommon in dzerent specimens of the same material ; and, as two of the results are hi&, and the other two low, there can be Iiatle doubt as to the general shape of the curve. This curve must, $here- fore, be regarded more as indicating a general tendency than tap a rigid represenbtion of fact. In Fig. 6 (p. 909 et seq.) we have full-sized skefches of tb b s t pieces after fracture. They are of interesi as showing thd gkea.flest plasticity is produced by the addition of a moderate amount of &kbn, say about 2-3 per cent.The following remasks were made by Professor Kennedy on the character of the test pieces :- 0 per cent. Surface smooth and silvery along planes of shear, very fine grained, and light in colour where fairly fractured. * This result, being somewhat irregular, was repeated.908 TURmR: THE INFLUENCE OF SILICON FIG 5.-XFFECT OF t?hLICON ON CAST IRON-CRUSHING STRENGTH-ON THE PROPERTIES O F CAST IRON. 909 FIG. &-FKTLL-SIZE SKETCHES SHOWIHG FRACTL*RES (Professor Kennedy).910 TURNER: TEE INFLUENCE OF SILICONON THE PROPERTIES OF CAST IRON. 911 10 per cent. Si. 0.5 per cent. 1 per cent. In greatest part silvery, but at A close grained grey Very irregular, in part split longitudinally, part trans- Direct fracture as in crystals . versely, showing planes smooth and silvery.ake tch. 2 per cent. 2.5 per cent. 3 per cent. 4 per cent. Do. do. 5 per cent. Do. do. 7.5 per cent. Light grey, broken very irregularly, sound. 10 per cent. Light grey, fairly crystalline, irregular in texture, not quite sound. Before leaving this part of the subject, it may be well to refer to what has been urged as an objection to the results brought forward in this paper, namely, that they are in most cases exceptionally high. ‘This is illustrated in the following table :- Silvery grey ; at AA close grained grey crystals. Very slightly distressed on surface. Surface silvery along shearing planes. Tensile- Author. Woolwich, 1858.Fairbairn, 1853. Maximum . . 15.70 tons. 14.05 tons. - Minimum .. 4.75 ,, 4.85 y, Crushing- Maximum .. 92.54 ,, 58.42 ,, 95.9 tons. Minimum .. 34.10 ,, 22.54 ,, 40.7 ,, Maximum . . 7.719 ,, 7.268 ,, 7-530 ,, Minimum .. 6.924 ,, 6-886 ,, 6.771 ,, Specific gravity- In the second column are the results obtained at Woolwich in experiments conducted upon a large number of British irons, and published in the report “ Cast Iron Experiments, 1858,” p. 155. My attention was called to this report by Mr. John Spiller in June last, and I am obliged to him for introducing me to the most complete and interesting experiments on this subject with which I am acquainted. It is my intention shortly to refer t o these results in a separate paper, when I hope to show t h a t they furnish strong support of my own912 TURNER: THE INFLUENCE OF SILICON observations.It is necessary to explain how it was that these important experiments were previously overlooked. It is true that they are quoted in various text-books, including Watts’ Dictionary and Percy’s “Iron and Steel.” But in every case, so far as I am aware, the analyses and the mechanical tests were separately referred to, and, only recently being able to obtain access to the report itself, I had no reason to connect the mechanical tests recorded in one place with the chemical analyses published in another. In considering the objection previously mentioned, however, it must be remembered that special care was taken in my experiments to prepare iron unusually free from the ordinary impurities, and that the carbon is always uniformly low for cast iron.Hence we should naturally expect the maximum results to be somewhat higher than usual. There would be more force in the objection if the results had been lowel. than usual, since then the tests might have been considered untrustworthy ; in the present instance, however, such a supposition is evidently quite out of the question. If now the various curves which have been given in this paper be examined the following conclusions may be drawn :- 1. That a suitable small addition of silicon to the cast iron pre- viously almost entirely free from silicon is capable of producing a considerable improvement in the mechanical properties of the metal. 2. That the amounts of silicon capable of producing the maximum increase are probably as follows :- For crushing strength .. . . . . . . . . about 0.80 per cent. ,, modulus of elasticity.. . . . . . . ,, 1.00 ,, ,, specific gravity (in mass). . . . ,, 1-00 ,, ,, softness and working qualities ,, 2.50 ,, ,, tensile strength . . . . . . . . . . . . 7 , 1-80 9 , 3. That in cast iron where general strength is required the amount of silicon should not vary much from about 1.4 per cent.; but that when special softness and fluidity are required about 2.5 per cent. may be added. Even in tlhe latter case, however, any increase beyond 3 per cent. must be dangerous. In connection, however, with the above statements, it must be remembered that any considerable quantity of other elements, besides carbon and silicon, will materially affect the properties of the metal, and probably also the amount of silicon which should be present, in order to produce any desired character.The results are only strictly true under the circumstances of my experiments, and a careful com- parison of the results of a large number of observations upon different kinds of iron will be necessary before the conclusions drawn may beO S THE PROPERTIES OF CAST IRON. 913 considered absolutely trustwol=thy. Upon this work, I am at present engaged. At the Glasgow meeting of the Iron and Steel Institute in Septem- ber last, an interesting paper was read by Mr. Charles Wood, in which it was shown that by a suitable addition of siliceous pig iron to Cleveland iron, castings of softer character could be obtained.Mr. Wood also showed that by adding silicon t o white cast iron the metal passed gradually into soft grey iron with increased tenacity, thus confirming the results given in my previous paper. The addition of siliceous iron wag carried on during several months’ working, running 60 t o 70 tons per day, and satisfactory results were obtained. Mr. Wood recommends that for castings where strength is required the silicon should be about 1% to 2.0 per cent., while for soft, sharp, clean castings about 2.6 to 3 per cent. of silicon is preferred. These numbers are in each case about $ per cent. higher than those deduced from my experiments, and the difference probably depends upon the phosphorus present in Cleveland iron. Since my paper was written I have received the following note from Mr.Wood :- “ I am still using silicon pig largely in the fouiidry, and since reading my paper have sold several lots to different founders, who speak very favourably of the softening effect. I think myself, on further experiments, that my percentages are rather high. For strong iron 1.5 t o 1.75 per cent. would be nearer, whilst 2.5 to 2.75 might be taken for softness, although 3.00 will do no harm, as in many classes of castings softness is of greater importance than a slight decrease of strength.” I may now perhaps be allowed t o say a few words as to the cause of the changes which silicon produces when added to pure cast, iron. It has long been observed that certain kiiids of grey iron, when quickly cooled, may be hardened, their specific gravity increased, and their character changed, from grey t o white.On the other hand, certain white irons when strongly heated, and afterwards allowed to solidify slowly, become converted into grey iron, which, on account of its greater liquidity and softness, is preferred for many purposes. But it has been shown by Dr. Percy (“Iron and Steel,” p. 117) that certain kinds of grey iron cannot be rendered white by chilling ; and this fact is confirmed by Ledebur; on t’he other hand, Percy was unable 150 change some kinds of white iron into grey, even by a very high temperature and subsequent slow cooling (p. 121). Hence though in the majority of cases the question of white or grey iron may be settled by the circumsttances of temperature and rate of cooling, yet in other instances it depends on chemical constitution, and the character of the metal can only be changed by altering the chemical914 TURNER: THE INFLUENCE O F SILICON composition.Irons which are permanently white are rich in manga- nese or sulphur, but deficient in silicon, whilst irons that are perma- nently grey are probably rich in silicon and poor in manganese and sulphur. Thus No. 1 dark grey iron, which is highly graphitic and generally also rather highly siliceous, is found to be quite unsuitable for the production of chilled castings, whilst the iron which is found most suitable for this purpose is “ strong,” usually No. 4 or 5, and cont,ains either a relatively small proportion of silicon, or a large proportion of manganese or sulphur. If we examine into the relationship between temperature and composition, we find that a high temperature, which is found to be necessary for the production of a graphitic iron, is also the most suitable for the reduction of silicon ; whilst, on the other hand, the low temperature necessary for the pro- duction of white iron lowers the amount of silicon but favours the absorption of sulphur.” It would seem, therefore, that the character of the iron depends not on the temperature alone, but also on those chemical changes which accompany the alteration of temperature. In this connection I have examined the composition of more than 180 specimens of pig iron, as shown by analysis, a few of which are original, but the great majority have been selected from the works of Percy, Abel, Lowthian Bell, and others.The lowest percentage of silicon found in a specimen of British grey pig iron is 0.81, whilst the highest percentage of silicon in any specimen of white iron, not con- taining an abnormal quantity of either sulphur or manganese, is under 1 per cent. It must be mentioned, however, that in the case of foreign irons this difference is not quite so plainly marked ; and further, that analyses performed 30 years ago or upwards have been rejected, as possibly misleading ; whilst some doubtful cases have also been omitted in which the analyses were more o r less incomplete. It is not contended that the rule has no exceptions; but it is believed that the general fact has been proved, without the slightest doubt, in the case of British irons. Now, as no other constituent varies in the same manner as silicon has been shown to do, we are justified in con- cluding that the effect noticed is due, in great part, t o a difference in the proportion of silicon present.It has even been stated, on the authority of Karsten and others, that in castings of grey iron the outer chilled portion contains more carbon and less silicon than the inner grey portions. I do not contend that this explanation of the cause of the difference of the method of occurrence of carbon in cast iron is new. On the contrary, reference has already been made to the observation of Sefstrom, mentioned by Dr. Percy, “ that the carbon in grey iron, in which much silicon exists, say from 2 to 3 per cent., is wholly or * I, Lowthian Bell. “Iron and Steel,” p.416.ON THE PROPERTIES OF CAST IRON. 915 nearly so, in the graphitic state.” And, 30 years ago, Messrs. Price and Nicholson at the works of the Lilleshall Iron Company, were producing iron by a patent process in which grey iron of good chemical quality was melted with the product of the finery forge in proportions regulated by the applications the procluct was to receive (No. 2618, November ZOth, 1855). In spite of these facts, and others of a similar kind, the close con- nection between the percentage of silicon and the mode of occurrence of carbon, did not appear to be understood. It is, however, very plainly seen in the two series of experiments conducted respectively by Mr. Wood and myself; although it must be boriie in mind that our conclusions are only true when manganese and sulphur are present in but small quantity, and when also the circumstances of temperature and rate of cooling are as far as possible uniform in the different specimens examined.These questions have been referred to at greater length on account of the interest attaching to the explanation of the results obtained in these experiments. Thus, at the Glasgow meeting of the Iron and Steel Institute, in September last, very considerable difference of opinion was manifested with regard to the question of the influence of silicon on the properties of cast iron. The opinion was expressed, and pretty generally endorsed, that “silicon or glazed pigs were always bad and unreliable, whatever they were mixed with,” and that “ as to silicon i n pig iron itself the less that could be had the better.” On the other hand, Mia.Stead agreed “that the less silicon they had in casting the better, provided that, practically, in the casting they kept the carbon in the graphitic condition.” And he has kindly expressed his opinion for me as follows : “ The strongest iron useful for genera,l foundry purposes is that which contains sufficient, silicon to prevent too large a proportion of the carbon remaining in the com- bined state in the iron when solidified.” I do not think there can be much doubt as to the truth of the result stated in the latter opinion of Mr. Stead, for not only does it agree with the deductions drawn from the experiments mentioned in the earlier part of this paper, but every practical man knows that the strongest iron is a close-grained grey, and one therefore which nearly approaches the limits of grey iron in the direction of mottled or white.But at the same time, in the present state of our knowledge, it appears unreasonable to attribute the whole effect to the action of silicon in rendering the carbon graphitic. What the action of silicon may be, when added to pure iron, in small but gradually increasing quantities, we do not know ; and, after numerous attempts to solve this question, I must confess myself no further advanced than when I first began. It appears much more reasonable to spppose the results916 TURNER: INFLUENCE OF SILICON ON CAST IROPT. we bave noticed as the sum of two influences, namely, that of silicon upon iron itself, combined with its influence in the production of graphitic carbon, than to assume that the whole effect is due t o the latter cause alone.Hitherto we have no experimental evidence to support the view that “ silicon is always bad ” in its effects on cast iron. On the contrary, there is much evidence of an opposite nature, quite apart from that furnished by my own experiments, for it is notorious that “refined metal,” which is of special chemical purity and contains only a few tenths per cent. of silicon, is quite unsuit- able for foundry purposes, being deficient in tensile strength, too hard for working, and often unsound. Further, although we find that, in the presence of silicon, a low percentage of combined carbon always accompanies a strong iron, we do not find that the strongest iron has the Zowest combined carbon, as we should expect if the result TT-ere due merely to the separation of graphite. This is illustrated both in the analyses b7 Mr.Stead, and also in those I have previously given (this vol., p. 581). Again, on examining Fig. 5 (p. 908) it will be seen that the effect produced by the addition of silicon is regular and progressive. We find that up to 1 per cent. the improvement is quite obvious alike in crushing strength, modulus of elasticity, and tensile strength. though this improvement is n o t accompanied by the separation of graphite; between 1 and 2 per cent. we have the strongest iron, accompanied by much graphitic carbon ; with upwards of 2 per cent. we have inferior iron, though the gradual deterioration in quality is not accompanied by any regular increase in combined carbon ; on the other hand, this distinctly decreases in quantity as the metal becomes weaker. Or, to state the matter in another form, if the effect noticed is wholly due to the separation of graphite, then the percentages of graphite, if expressed in a curve, should be of the same general shape as those curves we have given in Fig. 5 ; as this is not the case, we are justified in concluding that the separation of graphite is but a part of the effect produced by silicon, and not the whole effect. It is there- fore probable that the improvement in the mechanical properties of cast iron, produced by the addition of silicon, is owing partly to a direct beneficial effect due t o suitable proportions of silicon itself, and partly to a secondary influence which silicon exerts on the carbon present. I n conclusion, it may be added that 1 hope shortly to be able to bring forward evidence based upon the researches of Pairbairn, Abel, and others, t o support the conclusions I have already drawn, and t o show how far the results given in this paper aye confirmed, or modi- fied, by the teaching derived from the study of a large number of independent and most carefully conclucted experimeuts.

ISSN:0368-1645    

DOI:10.1039/CT8854700902

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

917 L X X X I V . - O n the Relation of Diaxobenaeneanilide to Anzidoazobenzene. By R. J. FRISWELL and A. G. GREEN. IN the year 1862, Griess (Annalen, 121, Z57), who had four years previously given to the world the first of that remarkable series of researches on the “ substitution of nitrogen for hydrogen in organic amido-compounds,” which has since proved the parent of so mauy discoveries, first turned his attention to the study of his reaction upon organic bases. The first compound discovered was that to which Griess gave the name of “ diazoamidobenaol” (Zoc. cit., 258),* and it was prepared by passing a stream of nitrous gas through aniline dissolved in from six to ten times its weight of alcohol in the cold. In the following year the first azo-colouring matter made its appearance as a commercial article under the name of “ a n i l i n e yelZozu,” from the works of Nessrs.Sinipson, Maule, and Nicholson. It was prepared by a process devised by the late Mr. Frederic Field, F.R.S., which consisted in the passage of a stream of nitrous gas from nitric acid and arsenious oxide, through aniline or aniline dissolved in alcohol. The subsequent steps were the recovery of the alcohol and unaltered aniline by steam distillation, first alone and then with caustic soda, the solution of the base in alcohol, and its separation from tarry matters, and finally the conversion of the alcoholic solution of the base into the oxalate by the addition of oxalic acid. The constitution of this substance was, it need hardly be said, quite unknown, and its preparation was entirely empirical.In 1866, Griess and Martius (Zeit. Chem., 1866, N.S., 2, 132) pub- lished a paper in which the first amidoazo-compounds were described. They were aware oE the fact that aniline yellow was prepared in some way by the action of nitrous gas upon aniline, and believed it to be identical with Griess’s “ diazoamidobenzol.” Requiring a large quantity of the latter, they purchased aniline yellow and commenced t o purify it, discovering directly that it was not diazobenzene- anilide, but that it was the oxalate of a base, the empirical formula of which was identical with that of diazobenzeneanilide. They showed that on reduction it split up into paraphenylenediamine aiid aniline, and accordingly e v e it the constitutional formula CsH,*N2* CsH5*NH2, and called it “ amidoazobenzol.” They also found that a colouring matter manufactured by Messrs.* We propose throughout to call this body diazobenzeneanilide, following a paper by A. Sarauw (Bet-., 14, 2443). suggestion in a note to VOI’. XLTII. 3 s918 FRISWELL AND GREEN ON THE RELATION OF J. J. Muller and Co., of Basle, by the action of stannate of soda upon nitrate of aniline in boiling Bolution consisted essentially of the same product, and as they found phenol to occur as a bye-product in both processes, they were led to believe that the action was on the whole an oxidising one as follows :- 3CSH7N + 30 = C12H,,N, + CeHbO + 2Hz0, and they decided that the production by the nitrous gas process was only a question of temperature, the one isomeride, diazobenzene- nnilide, being produced in the cold, the other, amidoazobenzene, when the reaction took place in a warm solution (Zoc.cit., 133). I n the same year Kekul6 (Zeit. Chem., 1866, N.F., 2, 688) showed that diazobenzeneaniline, if left in contact with a solution of an aniline salt, spontaneously changed into amidoazobenzene after an interval of two or three days; moreover he observed that the first effect of the action of nitrous gas on aniline in alcoholic solution was to produce diazobenzeneanilide, and he rightly accounted for the formation of phenol by ascribing it to the decomposition of that compound. Kekul6 suggested that the change from one isomeride to the other was in reality a case of double decomposition, and observes in the coiirse of his paper that since one of the products of this change is aniline hydrochloride, a small quantity of an aniline salt ought theoretically to convert a very large quantity of the anilide.I n 1875, Baeyer and Jaeger (Ber., 8, 151) prepared diazo- benzene - ethylamide and diazobenzenedimethylamide, compounds analogous to diazobenzeneanilide, in which the second half of the molecde was the residue of ethyl- or dimethyl-amine. These com- pounds they treated in alcoholic solution with aniline hydrochloride, and found that in both cases amidoazobenzene was produced, while ethylamine and dimethylamine hydrochlorides appeared as the corre- lative products of the reaction, thus greatly strengthening KekulB’s double decomposition theory, which was also further confirmed by Nietzki’s observation (Ber., 10,662) that paradiazotolueneparatoluide, reacting either with aniline or with orthotoluidine hydrochlorides, formed amidoazo-compounds with concurrent formation of para- toluidine hydrochloride.At this point the matter has been allowed to rest, the double decomposition theory being considered to com- prehend all the facts. In the course of some experiments undertaken with the object of obtaining amidoazobenzene directly, we have been led to question the validity of the received explanation of the cause of this isomeric change, for we think that the experiments we are about to describe throw considerable doubt upon it.DIAZOBESZENEAXILIDE TO AMIDOAZOBENZENE. 919 It will, we think, be readily conceded that if the received explana- tion is valid, there is no reason to suppose t'hat amidoaeobenxene could not under suitable conditions be formed directly by the combi- nation of diazobenzene with aniline hydrochloride. Acting on this supposition, me have endeavoured to obtain this reaction, b u t although we have varied the conditions in every possible way,both as to tempe- rature, acidity, concentration, solvent, order of mixture, and mass of reacting substances, we invariably found that diazobenzeneanilide was first produced. Conditions of Formation of Diaxobenzenean.ilide.Thus it is formed- (a.) By the action of a molecular proportion of sodium nitrite on one of aniline bydrochloride and one of aniline at any temperature between 0" and 90". (b.) By the action of an alkaline solution of diazobenzene hydrate on aniline.(c.) By the action of diazobenzene chloride on aniline a t 0" to 10". (d.) By the action of diazobenzene chloride on aniline suspended in boiling water. B u t if the product of the reactions c or d are left for a few hours in the solutions in which they are formed, they are slowly converted into amidoazobenzene chloride. (e.) Sodium nitrite added to aniline in solution in excess of strong or dilute acetic acid produces diazobenzeneanilide. (f.) Sodium nitrite in fine powder added to a solution of aniline in toluene with excess of acetic acid produces diasobenzeneanilide. (9.) Sodium nitrite added to excess of aniline hydrochloride or of any mixtiire of aniline and aniline hydrochloride, no matter how great the mass, always produces diazobenzeneanilide.It will thus be noticed that in every case this compound was pro- duced as a first product, even when, as in cases c, d, e, and g, it WiLS formed in the presence of excess of aniline hydrochloride or of an acid, although under such conditions a second reaction slowly takes place with the production of the isomeric compound, We have shown that the change is in no way a function of tempera- ture, acidity, or of the presence of aniline hydrochloride alone, since diazobenzeneanilide is formed first under all circumstances. It is extremely difficult to understand this transformation of a compound under conditions which are precisely the same as those which attend its production ; indeed the phenomena appear to us more to resemble the birth and death of an organism than any other change with which we are acquainted among chemical substances.Since the920 FRISWELL AND GREEN ON THE RELATION OF diazobenzeneanilide is formed in the presence of aniline hydro- chloride, why should it, apparently by mere lapse of time, change into the isomeric substance ? If the latter is (and it undoubtedly is) the more stable compound, why should it not form a t once, and why docs it only arise as a subsequent stage in t,he history of the trans- formation of a less stable compound ? Conditions of the Reacting Bodies during the Change. Diazobenzeneanilide was prepared in the usual way, thoroughly washed with dilute acetic acid and then with water, dried, twice recrystallised from pure benzene, and then three times from alcohol ; its m.p. was 96". One molecular proportion ( 5 grams) of this was suspended in cold dilute hydrochloric acid containing 0.91 gram HC1 (1 mol.). Under these conditions we found that in the course of from 12 to 15 hours it is converted into amidoazobenzene chloride mixed with tarry substances and phenol. The latter is due to the decomposition of diazobenzene chloride, for during the whole of the time we were able by appropriate treatment to prove the presence in solution of diazobenzene chloride and aniline hydro- chloride. After extracting the solid product with toluene to remove tarry substances, pure amidonzobenzene chloride was left in steel- blue needles, the yield being 2.5 grams or 50 per cent. It thus appears that diazobenzeneanilide in the presence of hydrochloric acid is decomposed into diazobenzene and aniline hydrochloride, which then slowls reunite in a different way to form amidoazo- benzene.When excess of acid is employed, complete solution of diazobenzene- anilide ensues, the substance being resolved into diazobenzene and aniline chlorides, which are prevented from again uniting by the excess of hydrochloric acid, the neutralisation of which reprecipi- tates diazobenzeneanilide. If metaphenglenedianine is added before nzutralisation diamidoazobenzene (chrysoydine) is formed. The pre- sence of aniline hydrochloride, ammonium chloride, or zinc chloride in the acid solution, does not appear to iiifluence the change in any way whatever. The higher the temperature, the more rapid is the change, and the greater the proportion of tarry decomposition prodncts.The experiment was carefully tried on a very considerable scale, as much as 2 o r 3 kilos. of diazobenzeneanilide being employed. The substitution of acetic for hydrochloric acid retarded the action, and gave rise to increased decomposition. Zinc chloride and ammo- nium chloride solutions produced no change. A molecular propor- tion of nitric acid acted in almost the same way as hydrochloric acid,DIAZOBENZENEANILIDE TO AMIDOAZOBEXZEXE. 921 whilst half or even one molecular proportion of sulphuric or oxalic acid diluted produced scarcely any change. The latter fact appears to be opposed to the theory that might be advanced, that the presence of an acid tends to induce the formation of a base to combine with it, since we should expect that this ten- dency would be increased by using strong acids, such as sulphuric and oxalic acid, instead of hydrochloric acid. I n alcoholic solution, the conversion of diazobenzeneanilide into its isomeride is, as is well known, caused in the cold by aniline hydro- chloride.We have found that the same result is produced by the action under like conditions of zinc chloride, and more slowly and on heating by calcium chloride. During all these reactions, whether in alcoholic or aqueous solu- tion, some evolution of nitrogen always occurs, some of the anilide or rather the diazobenzene produced by its resolution being converted into phenol and tarry substances. It thus appears that diazobsnzeneanilide is capable of being con- verted into its isomeride by treatment with one equivalent of an acid, such as bydrochloric acid, or of any unstable salt ca,pable of furnishing the acid required, such as aniline hydrochloride, zinc chloride, cal- cium chloride, &c.Hence we consider the double decomposition theory proposed by Kekul6, and considered to have been proved by the researches of Baeyer and Jaeger and of Niehki, as untenable ; the conversion of the diazobenzeneanilide into amidoazobenzene in the ordinary manner by treatment with aniline hydrochloride dissolved in aniline is, as we consider, entirely due to the hydrochloric acid present, and has nothing to do with the aniline, which merely serves as a convenient solvent, and by its presence prevents the decomposi- tion of the diazobenzene, which is formed as an intermediate product by the resolution of the diazobenzeneanilide previously to its recom- bination in a different manner to form the isomeride.The formation of arnidoazobenzene, by treating diazobenzene-ethylamide and diazo- benzenedimethylamide with aniline hydrochloride, can be easily explained in a similar way ; the hydrochloric acid first resolves thPm into diazobenzene and ethylamine or dimethylamine, m d the diazo- benzene then combines with the aniline present to form amidoazo- benzene. The same remark applies also to Nietzki’s observations on the actions of aniline and orthotoluidine hydrochloride on paradiazo- tolneneparatoluide. From the above experiments, it would appear that diazobenzene- anilide, under the influence of hydrochloric acid or of an unstable chloride, is resolved into its constituents, and that the diazobenzeiie thus produced is campable of slowly recombining with aniline hydro- chloride to form amidoazobenzene hydrochloride, although if the922 FRISWELL AND GREEN ON THE RELATION OF union is compelled to take place quickly by neutralising the acid, the anilide is reformed.It would thus seem that the coiiclusion that tin2e is required for the rearrangement of the molecule is irresistible. If the temperature is raised, the time required for the reaction is greatly diminished (though we have never Rucceeded, a t any temperature, in getting an instantaneous reaction in this direction), but, or'r the other hand, the amount of destructive decomposition is greatly increased.Beyond the fact of the necessity of this time interval, we cannot offer any further explanation of this moot remarkable reactlion or rather chain of reactions. The fact that diazobenzeneRnilide is formed by the direct combina- tion of diazobenzene chloride and aniline, and that, the product, when left in the solutlion in which i t was formed under exactly the same conditions under which it was formed, by mere lapse of time appa- rently is again resolved into its constituents, and that these con- stituents again unite, but in a difFerent manner, to form amidoazo- benzene hydrochloride, is to us, at present, perfectly inexplicable, and we consider that it stands quite apart from the generality of chemical cbanges. If the diazobenzeneanilide is destined to be again resolved into its constituents, why should it be formed ? And if diazobenzene chlovide can combine with aniline to form amidoazobenzene, why does it not do so in the first place ? It has been suggested by Baeyer and Caro ( B e y ., 7 , 966) that diazobenzene can slowly change into the isomeric compound nitroso- aniline, C,H,(NO).NH,, and that it is by combination of the latter with aniline that amidoazobenzene is produced. If this theory were correct, it would certainly help to explain the mystery, but it is open to the objection that it would make the formation of amidoazobenzene take place in quite a, different way from that of di- and tri-amidoazo- benzene and all other azo-compounds that are formed directly, or else necessitate tlie alteration of the received constitution of these compounds.diamine, the symnietrical diamidoazobenzene, 1 4 For instance, by the action of nitrosoaniline on metaphenylene- . NHs would be produced, sImmetrica.1 formula whereas chrysoydine undoubtedly has the un-DIAZOBENZENEANILIDE TO AMIDOAZOBEKZENE. 923 for on reduction, it yields aniline and 1 : 2 : 4 triamidobenzene ; whereas the first compound would yield paraphenylenediamine and metaphenylenediamine in equal molecular proportions. The resolutiou of diazobenzeneanilide into diazobenzene and aniline explains many facts which have been observed by Griess and others. Thus it was by the action of bromine upon diazobenzeneanilide that Griess in one of his earlier papers (Proc. Roy. Xoc., 13, 376) prepared diazobenzene as the bromide, tribromaniline being formed as the cor- relative product.The reaction no .doubt consisted in the resolution of the anilide into diazobenzene and aniline, the latter being further attacked by the excess of bromine and thus removed. Again, Griess (Proc. Roy. Soc., 12, 418) first obtained diazobenzene nitrate by treating diazobenzeneanilide with nitric acid containing nitrous acid, in which case t,he nit& acid would resolve the anilide into diazobenzene nitrate and aniline nitrate ; the latter would then be attacked by the .nitrous acid and also be converted into diazo- benzene nitrate. The formation of phenol during the preparation of amidoazobenzene by various processes, and by the decarnposition of diazobenzene anilide by acids, has been qpeatedly observed, and its source is now clear.Formation of Bitcmidoazobenzene and Homologues fyom Diazo- benxeneanilide. 20 grams (1 mol.) of pure diazolenzeneanilide was warmed for several hours with an aqueous solution of 16 grams (1 rnol.) meta- tolylenediamine hydrochloride. On boiling the mixture, aniline and water distilled over, and the solution contained the hydrochloride of diamidotol ueneazobenzene (tolylenediaminechryso'idine) ; it was fil- tered, and on cooling the chrysoydine crystallised out. The yield was 24 grams, or 96 per cent. of the theoretical quantity. The reac- tion takes place in exactly the same way with metaphenylenediamine, and also occurs, though much less perfectly, a t the ordinary tempe- rature. The tolylenediamine was employed, as it can be very readily obtained in a pure state.We consider the mechanism of this reaction t o be exactly the same as with those previously described, the diazobenzeneanilide being first resolved by the acid and the diazobenzene formed combining with the diamine. Resolution of Azoxybanzene. Wallach and Belli (Bey., 13, 525) have found that nzoxybenzene, by treatment with sulphuric acid, is converted into the isomeric com- pound oxyazobenzene. It appears to us extremely probable that this924 DIVERS AND NAKAMURS : NEW HYDROCARBON reaction is strictly analogous to the isomeric conversion of diazo- benzeneanilide, and that similarly to the latter the azoxybenzene is first resolved into diazobenzene and phenol, which then reunite to form oxyazobenzene. A further cmclusion from this would be that probably diazobenzene- anilide and azoxybenzene have an analogous constitution. V. Meyer, in a note appended to a paper by A. Sarauw (Bey., 14, 2447), has pointed out that diazobenzencanilide must have a symmetrical struc- ture, which the ordinary formula, C6H,*N : N*NH-CsH,, does not express. It appears to us that the symmetricd formula, CsH5*N-N*CsH6, ‘NG analogous to azoxpbenzene, CsH5*N-N*C6H,, has greater probability, \/ 0 and, so far as we can see, is not open to cbjection. There remains, among other points in connection with thiR research, which we hope to continue, one deeply interesting branch, which we are unable to pursue, as we have neither the necessary apparatus nor the requisite t’ime at our command. We allude to the questions relating to the heat of formation of diazobenzeneanilide and of amido- azobenzene, and to the other somewhat complicat,ed heat problems which these reactions present. We trust that a study of them may be undertaken by abler hands than ours. In conclusion, we have to express our thanks to Messrs. Brooke, Simpsoc, and Spiller, i n whose laboratories at the Atlas Works the work herein described was carried out.

ISSN:0368-1645    

DOI:10.1039/CT8854700917

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年代:1885

数据来源: RSC

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924 DIVERS AND NAKAMURS : NEW HYDROCARBON LXXXV. - On an Ai7parenfly N e w Hydrocarbon from Distilled Japanese Petroleum. By EDWARD DIVERS and TEIKICHI NAKAMURA, Imperial College of Engineering, Tdkio, Japan. A VISIT that we made to the petroleum wells at Sagara in the pre- fecture of Shizuoka, Japan, last year, led to our attention being drawn to a solid yellow substance which occurs in the very last portions of the distillate from the petroleum. These portions consti- tute an almost solid brown grease with green fluorescence. When treated with light petroleum oil, this grease leaves a yellow bulky friable mass of a dull greenish shade, from which a bright yellowFROM DISTILLED JAPANESE PETROLEUN. 925 pulverulent substance may be obtained. Like other similar products, however, the yellow substance can be separated into a white one and a very small quantity of a yellow one not yet examined.The white or yellow substance is a hydrocarbon, distinct apparently from any yet described. The purified hydrocarbon is amorphous in appearance, but when deposited from a benzene solution forms minute crystals. From acetic acid, it is more distinctly crystalline, and on drying is of a whiter colour and d k y lustre. It is denser than carbon bisulphide, highly electric when dry, and when prepared in the way adopted, has a bright yellow colour. This colour, however, as mentioned above, is due to a matter adhering in minute quantity to the main product; the latter may be deprived of colour, more or less completely, by cooling its hot solution in benzene or acetic acid after it has been exposed for some time to the sun.The yellow colouring matter in solution is thereby changed, but only slowly, into an orange-red and still soluble matter, and in this respect differs from the chrysogen of coal-tar which is bleached by the sun. Both the yellow and the white modification of the hydrocarbon can be sublimed almost unchanged in a vacuum, but with difficulty. When heated in the air, it darkens and is partly decomposed, appa rently by oxidation. Its melting point is accordingly not sharply defined, and lies between 280" and 285". Boiling heavy ben- zene dissolves about 2 per cent., and carbon bisulphide, ether, chloro- form, glacial acetic acid, light petroleum, and alcohol also dissolve more or lesk. When a cold ethereal solution of the yellow form of the hydro- carbon is poured on to a filter-paper, the edges and upper part of the filter soon throw out, in consequence of the eraporntion of the ether, a crystalline arborescence, several millimetres high, which is of a pure white colour.Shortly after its formation, the spicules of this arbores- cence suddenly shrink up, one by one, and resume the original bright yellow colour. This series of phenomena is very striking. Cold sulphuric acid gradually changes it to a bright brown floccn- lent substance, probably a quinone. Moderately heated, it dissolves in the acid to a fine deep chromium-green coloured liquid, which becomes indigo-blue when more strongly heated. Poured into water, neither the green nor the blue solution deposits any iiisoluble matter.In hot glacial acetic acid, chromium trioxide rcadily forms a flocculent orange-red quinone, readily converted to 5 colourless soluble substance by the further action of the chromium trioxide. The quinone is brown when dried, and is but little soluble in benzene, chloroform, or alcohol. There is no good solvent for the hydrocarbon. VOL. XLVII. 3 1926 DIVERS AND NAKAMURA : NEW HYDROCARBON. Nitrio acid acts slightly on the hydrocarbon, converting it appa- rently to its quinone, or to a nitroquinone, very little soluble in the acid. Picric acid forms a reddish-brown, slightly crystalline compound with the hydrocarbon, whieh is decomposed by washing with alcohol or with water. Bromine acts moderately on the hydrocarbon, evolving hydrobromic acid and yielding a bromine-derivative of the hydrocarbon, soluble both in chloroform and benzene.It is a brown substance, not yet obtained in the crystalline state. Both yellow and white forms of the hydrocarbon have been burnt €or analysis, with results which correspond to those calculated for nC4H3, where n is perhaps 6 :- Yellow. White. v - 7 7-7 I. 11. 111. IV. v. C4H3 Carbon . . . . 94.10 94.08 94.15 94.13 94.10 94.12 Hydrogen.. 5.99 5.98 5.88 6.10 6.08 5.88 100.00 The hydrocarbon, " petrocene," which Heinilian obtained in 1877 from Pennsylvanian petroleum, is not only like ours in origin, but also in several of its properties. It melts, however, above 300°, is almost insoluble in ether, and the formula assigned to it is Cs2Ha2.* Prunier and David's hydrocarbons, which in 1877 had been exhibited as petrocene, scarcely need any consideration.One of the hydrocarbons which Sadtler and McCarter examined in 1881 agrees with ours in melting point, but differs in composition, having the formula CIsHl4 = carbon 93.2 per cent. Picene somewhat resembles our hydrocarbon, but differs in its melting point (330-335") ; in being capable of distillation in absence of oxygen ; in its distinct crystalline form; its solubility in many solvents being less; solubility of its quinone in chloroform, &c.; and in its crystalline and insoluble bromine-derivative, Beneerythrene, described by Schultz, is some- what like our hydrocarbon, but melts at 30'7--308",,and is soluble in cold nitric acid. Others are too remote from ours in properties to require consideration. We hope to be able to extend our examination of this hydrocarbon from Japanese petroleum, and to give a more precise account of its properties than in this preliminary notice. f C32H22 has 0.46 more carbon and 0'46 less hydrogen than C,H3.

ISSN:0368-1645    

DOI:10.1039/CT8854700924

出版商:RSC    

年代:1885

数据来源: RSC

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INDEX OF AUTHORS’ NAMES. T R A N SAaC T I 0 N S. 18 8 5. A, Anschiitz, R., a new method of pre- paring aromatic hydrocarbons, 898. Anschiitz, R., and Q. W i r t z , on the decomposition of aromatic ethereal salts of fumaric acid, 899. A r m s t r o n g, H. E., constitution of the fulminates, 79. A t k i n s o n , G. T., obituary notice of, 329. B. sodium and their analogues, 353. gases, 34Y. B a k e r , H a r r y , the ortho-vanadates of B a k e r , H. B., combustion in dried U l a i k i e , Dr. A., obituarynoticeof,330. B l o u n t , B., on the cause of t h s de- crepitation in samples of so-called explosive pjrites, 593. cerite metals, 111, 879. Brown, H. T., and (3. H. M o r r i s , on the non-crystallisable products of the action of diastase on starch, 527. B r 11 n t o n, T.L., on the physiological action of brucine and bromostrych- nine, 143. 3 ..‘ Irtuiier, B., the chemistry of the C. C a r n e l l e y , T., and A. Thomson, brominated derivatives of diphenyl, tolylbenzene, and ditolyl, 586. Cook, E. H., detection and estimation of iodine, 471. C u n d a l l , J. T. See Ramsay. D. D e s s a i g n e s, V i c t o r, obituary notice of, 309. Divers, E., on the constitution of ful- minates, 77. - the constitution of some non-satu- rated oxygenous salts and the reaction of phosplrorus oxychloride with sul- phites and nitrites, 205. Divers, E., and T. Haga, conversion of Pelouze’s nitrosulphates into hypo- nitrites and sulphites, 203. -- on the behaviour of stannous chloride towards nitric oxide and towards nitric acid, 623. -- tlie existence of barium and lead aitrosulphates, 364.-- the formation of hyponitrites from nitric oxide, 361. Divers, E., and M. Kawakita, on the decomposition of silver fulminate by hydrochloric acid, 69. Divers, E., and T. N a k a m u r a , on an apparently new hydrocarbon from dis- tilled Japanese petroleum, 924. Divers, E., and T. S h i m i d z u , on the action of pyrosulphuric acid on oer- tain metals, 636. -- on tlie constitution and re- actions of liquid nitric peroxide, 630. -- reactions of selenious acid with hydrogen sulphide, and of sul- phurous acid with hydrogen selenide, 441. -- the Epecific action of a mix- Lure of sulphuric and nitric acids on zinc in the production of hy- dToxylaniine, 597. D i r e r s , E., and M. Shimos6,a new and simple method for the quantita- tive separation of tellurium from selenium, 439.Dixon, IT. B., and H. F. Lowe, the decomposition of carbonic acid gas by the electric spark, 571. Dobbin, L., aiidO. Masson, action of the halogens on the salts of trimetlyl- sulphine, 56.928 INDEX OF AUTHORS. Dumas, J. B. A., obituary notice of, 310. F. F o r r e s t , J., obituary notice of, 331. F r a n c i s , E. E. H., toughened filter- papers, 183. F r a n k l a n d , E., on chemical changes in their relation to micro-organisms, 159. F r a n k l a n d , P. F., the illuminating power of hydrocarbons, 235. Friswell, R. J., arid A. G. Green, on the relation af diazobenzeneadide to amidoazobenzene, 917. G. Gilbert, 3. H. See Lewes. Gladstone, J. H., and A. TPibe, on the action of the copper-zinc couple on organic bodies, Part X, on bro- mide of benzyl, 448.Green, A. 8. See F r i s w e l l and Morley. Griess, P e t e r , and G. IE. E a r r o w , presence of choline in hops, 29% G r i f f i t h s, A. B., on the application of iron sulphate in agriculture and its value as a plant food, 46. G u t h r i e , F. B., on the solubility of certain salts in fused sodium nitrate, 94. H. Raga, T. See Divers. Harrow, (2. H. See Griess, H a r t l e y , W. N., on the relakion between the molecu1:w structure of carbon-compounds and their absorp- tion spectra. Part VII, 685. Harvey, R., obituary notice of, 331. Hudson, J. W., obituary notice of, 331. J. James, J. W., derivatives of taurine; - on acetoacetic ether, 1. - preparation of ethylene chlorothio- cyanate and P-chlarethylsulphmic acid, 385.Part I, 367. J a p p , F. R., and N. H. J. Miller, on additive and Condensation compounds of diketones with ketones, 11. J a p p , F. R., and Miss M. E. Owen?, on condensation compounds of benzil with ethyl alcohol, 90. J e n n i n g s , F. M., obituary notice of, 332. Jones, W. R., obituary notice of, 332. K. Kolbe, A. W. H., obituary notice of, 323. Lansdell, M. J., obituary notice of, 332. Eawes, S i r J. B., and J. H. Gilbert, on some points in the composition of soils ; aikh results illustrating the sources of the fertility of Manitoba prairie soils, 380. Lowe, H. F. See Dixon. Lunge, G., on the existence of nitrous anhydride in the gaseous state, 457. - on the reaction between nitric oxide and oxygen under varying con- ditions, 465.M. Masson, 0. See Dobbin. Meldola, R., on secondary and tertiary azo-compounds, No. 111, 657. - on the constitution of the haloyd derivatives of naphthalene (fourth notice), 497. Meyer, L., and I(. S e u b e r t , on the unit adopted for the atomic weights, 426. -- the atomic weight of silver and Prout’s hypothesis, 434. Mi e r s, H. A., crystallography of bromo- strychnine, 144. - crystallography of CuS04,2CuH202 (Supplement to XLI), 377. Miller, X. H. J. Morley, H. F., and A. G. Green, action of zinc ethide on the benzoate of propylene chlorhydrin, 134. on the constitution of propy- lene chlorhydrin, 132. See J a p p . -- Morris, G. H. See 13 rown.INDEX OF 4UTHORS. 929 N. Nakamura, T. See Divers. h’apier, J., obituary notice of, 333. 0. Owens, Miss M.E. See J a p p . P. Pechmann, H. v., and W. Welsh, formation of pyridine-derivatives from malic acid, 145. Perkin, A. G., and W. H. Perkin, jun., on some derivatives of anthra- quinone, 679. P e r k in, W. H., jun., benzoylacetic acid and some of its derivatives. Parts I1 and 111, 240, 262. - on the synthetical formation of closed carbon-chains, 801. P e r k i n , W. H., jun. See also P e r - kin, A. Gt. Pickering, S. U., calorimetric deter- minations of magnesium sulphate, 100. -- on the heats of dissolution of the sulphates of potassium and lithium, 98. Pmrdie, T., action of sodic alcoholates on ebhereal fumarates and maleates, 855, R. Rammy, W., and J. T. Cundall, on the non-existence of gaseous nitrous anhydride, 672. -- the oxides of nitrogen, 18’7.Ramsay, mT., and S. Young, a method for obtaining constant tem- peratures, 640. -- on a new method of deter- mining the vapour-pressure of solids and liquids, and on the vapour-pres- Bure of acetic acid, 42. Richardson, Clifford, on the che- mical alterations in green fodder during its conversion inho ensilage, 80. Rogers, T. K., obituary notice of, 335. Roscoe, S i r H. E., on the spontaneous polymerisation of volatile hydrocar- bons at the ordinary abmospherie temperature, 669. S. S a k u r a i, J., on methylene chloriodide, 198. Senier, A., on formyl and thioformyl compounds derived from aniline and homologous bases, 762. S e u b e r t , K. See Meyer. Shenstone, W. A., a crystalline tri- - a modified Bunsen burner, 3’78. - alkalo’ids of nux-vomica. 111.Some experiments on strychnine, 139. cupric sulphate, 375. Shimidzu, 1’. See Divers. Shimosk, M. See Divers. S h n t e r , J. L., obituary notice of, Smith, R. Angus, obituary notice of, S m i t h , Watson. See Staub. Snap e, H. L., action of phenyl cyanate on polyhydric and certain monhy- dric alcohols and phenols, 7’70. Sorabji, K. B. B., on eome new par- aEns, 37. Staub, A., and Watson Smith, on certain derivatives of isodinaphthyl, 104. S t u a r t, C. M., on nitrobenzalmalonic acids, 155. 334. 335. T. Thomas, S. G., obituary notic2 of, 337. Thomson, A., colorimetric method for determining small quantities of iron, 493. Thomson. A. See a1m Carnelley. Thorpe, T. E., on the atomic weight -- on the sulphides of titanium, 491. Tribe, A. See Gladstone. T u r n e r , T., the influence of silicon on the properties of cast iron, 577, 902. - the selective alteration of the con- stituents of cast iron, 474. of titanium, 108. V. Veley, 8. H., on some sulp!iur com- VoeIcker, J. C. A, obituary notice of, pounds of calcium, 478. 339. 3 ~ 2930 INDEX OF AUTHORS. W. Warington, R., on the action of gypsum in promoting nitriseation, 758. W a t t s , Henry, autobiography of, 342. W e b s t e r, C. S. S., the chlorination of phloroglucol, 423. WellB, J. S., a quick method for tEe estimation of phosphoric acid in fer- tilieers, 185. Wigner, G. W., obituary notice of, 344. W i r t z , Q. See Anschutz. ~ W r i g h t , L. T., the illuminating power Wur t z, C. A,, obituary notice of, 328. of methane, 203. Y. P o s h i d a, H., chemical examination of the constituents of camphor oil, 779. Young, Sidney. See Eamsay.

ISSN:0368-1645    

DOI:10.1039/CT8854700927

出版商:RSC    

年代:1885

数据来源: RSC

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INDEX OF SUBJECTS. T R A N S A C TI 0 N S. 18 8 5. A. Absorption spectra, relation between the molecular structiire of citrbon com- pounds and their, Part VII, 685. Acenaphthalide, bromamido-, 603. - iod-, and iodonitro-, 523. - y-nitro-, Liebermann’s, bromina- Acenaphthaiides, nitro-, bromination of, Acetic acid, vapour-pressure of, 42. Acetoacetic ether and its derivatives, 1. Acetonebenzil and its reactions, 22. Acetonebenzilimide, 24. Acetonediphenanthraquinone, 20. Acetoneplienanthraquinone, formation Acetophenonebenzil, 25. Acetyltnethyltrimethylene, 852. Acety lmet hyltrimeth ylenecarboxylic Acetyltrimethylene, 834. Acetyltrimethylenecarboxylic acid and some of its salts, 831. Acids, apparent influence of temperature, time, dilution, and other conditions 011 the reaction between zinc and, 619.Alcohols, polyliydric and certain mon- hydrie, action of phenyl cyanate on, 770. Alkali stannites, inaction of, with nitrit,es and nitrates, 363. Alkaloids of nux vomica, 139. Allyltaurine, preparation of, 369. Ammonia, preparation of, from am- Ammonium nitrate and nitrit,e, heat- Aniline, vapour-pressures of, 647, 655. Annual general meeting, March 30tl1, Anthraquinone, an orthoquinone of, - some derivatives of, 679. tion of, 502. 499. and reactions of, 16, 17. acid, 851. monium sulphate, 1868. decomposition of, 236. 1885, 300. 684. Anthraquiraonemonosulphonic acid, dry distillation of the sodium salt of, 679. Antimony oxalate, use of, in printing, 1276. Aromatic hydrocarbons, new method of preparing, 898. Arsenious oxide, action of nitric acid on, 196, 197.Atomic weights, the unit adopted for, 426. Azobenzene, amido-, relation of diazo- benzene anilide to, 917. - diamido-, and homologues, forma- tion of, from diazobenzene anilide, 9%3. Azo-compounds, secondary and tertiary. researches on, No. 111, 657. Azoxybenzene, resolution of, 923. 3. Balance-sheet of the Chemical Society from March 24, 1884, to March 23, 1885,347. -- Research Fund from March 24, 1884, to March 23, 1885, 348. Barium nitrososulphate, existence of, 364.. Benzalmalonic acids, nitro-, 155. Benzene, bromo-, vapour-presmres of, - chloro-, vapour-pressures of, 642, - description and measurement of Benzene-azo-a-P-naphthol, paranitro-, Benzene-azophenol, paranitro- and para- Benzene-azoresorcinol, paranitro-, par- Benzene-azosalieylic acid, paranitro-, and 646, 665.654. the spectrum of, 694. paramido-, 661. amido-, 658, 659- amido-, 660. paramido-, 666, 667. 3 T 3933 INDEX OF SUBJECTS. Benzil and acbtone, action of potash on a mixture of, 21, 27, 33. - and acebophenone, action of potash on a mixture of, 34, 35. - condensahion compounds of, with ethyl alcohol, 90. Benzoylacetic acid and some of its deri- vatirea, Parts I1 and 111, 240, 262. Benzoylacetonephenone, preparation of, 251. P-Benzoylhydrocinnamic acid, 32. Benzoj ltrimet,hylene, 840. - action of hydroxjlamine on, 844. Benzoyltrimdhylenecarboxylic acid, 'BC- tion of hydrobromic acid on, 842. I- - and some of its-salts, 836. Benzoyltriinethyleneoxime, 845. Benzyl bromide, action ot the copper- Benzylene, u- amd p-, and a aitro-deriva- Brucine, physiological action of, 143.Bunsen burner, a modified, 378. zinc couple 011, 448. tive of, 450. C. Calcium, some sulphur compounds of, - hydrosulphide, preparation of, in - sulphide, preparation of, in the dry - thiocarbonate, 486. Camphor oil, chemical examination of Camphorogenol, 793. Carbon bisulphide, vapour-pressures of, 653. - chains, closed, synthetical forma- tion of, 801. .- compounds, relation between the molecular struct,ure of, and their ab- sorption spectra, Part VII, 685. Carbonic acid ga5, decomposition of, by the electric spark, 571. Cast iron, influence of silicon on the pro- perties of, 577, 902. -- selective alteration of the con- stituents of, 474. Cerite metals, chemistry of, 111, 879. Cerium, atomic weight'of, 880.Cetane from cetyl iodide, 38. Chemical changes in their relation to Choline, presence of, in hops, 298. Ciniiamic acid, a-chloro-, formation of, from ethyl benzoplacetate, 257. - ethereal salts, aromatic, decomposi- tion of, by heat, 898. 478. the wet way, 485. way, 480. the constituents of, 779. micro-organisms, 159. Citrene from camphor oil, '787. Combustion in dried gases, 349. Constant temperatures, method for ob- taining, 640. Copper, action of nitric peroxide on, 633. - carbonate, basic, behaviour of, with nascent hydrogen, 1270. Copper-zinc couple, action of, on organic bodies, Pant X, on bromide of benzyl, 448. Corn ensilage, composition of, 52. Coumalanilidic acid, monomethyl salt of, Coumalmethamic acid, monomethyl salt 152. of, 15A D. Dehydracetic acid, constitution of, 277.Dehydracetonebenzil, 22, 26, 28. - reactions of, 29. Deliydracetonedibenzil, 26, 34. Dehydracetonephenanthraquinone, 17. Dehydracetonephenonebenzil, and action of bromine on it, 34, 36. Dehydrobenzoylacctic acid, action of phosphorous pentachloride on, 292. -- action of potsssic hydroxide on, 284. -- chloro-, preparation and pro- perties of, 292. -- constitution of, 294. -- preparation and properties of, -- reduction of, 287. Dehydrodiacetenephenan thraquinone, Dextrins, 527. - action of saccharomyces on, 565. - non-reducing, preparation of, 551. - separation of, 546. Djacctonephenanthraquinone, and the action of acetic anhydride on it, 15. Diallylacetoacetic ethers, certain mixed, 3. Diazobenzeneanilide, conditions of its formation, 919.- forrimtion of diamidoazobenzene and homologues from, 928. - relation of, to amidoazobenzene, 917. Dibenzoylacetic acid and some of its salts, 246. -- decomposition-products of, 249. Dii,enzoylmethane, prepmation of, 246, 249. Dibenzyl, form ttion of, from benzj 1 bromide, 453. 277. 16.INDEX OF SUBJECTS. 933 Dibenzylmalonic acid, 821. Dicetyl from cetyl iodide, 39. Diethyltaurine, preparation of, 3’71. Diheptyl from heptyl iodide, 40. Diketones, additive and condensation compounds of, with ketones, 11. Dimethylstilbene, 901. Diniet,hpltaurine, preparation of, 3’70.’ Dimethytaurocyamine, formation of, Diphenic acid, monobromo-, 591. Diphenyl, brominated derivatives of, Diphenylfurfuranedicarboxjlic acid, 3’744. 586. (ClsH!205), preparation and proper ties of, 266, 2’71.Dipyridine, descripf ion and measure- ment of the Fpectrum of, 717. Ditolyl, bromkated derivatives of, 586. - dibromo-, product of the oxidation of, 592. E. Egyptian sugar corn, analyses of, 88. Ensilage, chemical alterations in green fodder during its conversion into, 80, Ethane, illuminating power of, 235. - prepmalion of, 236. Ethoxysuccinic acid and some of its Ethyl aretoacetate, action of ethylene -- action of prvpylene bromide -- condensation of, with alde- - acetylacetoacetate, action of so- -- decomposition of, by water a t -- preparation and metallic de- - acetylmethyltrimethylenecarboxyl- - acetyl trimeth ylenecarhoxylate, 829. - alcohol, vapour-pressures of, 654. - allylbenzoylacetate, ?41. - allylmethylacetoacetate, prepara- - benzalbenzoylacetate, preparation - benzoylucetate, action of ethylene -- action of phosphorus penta- -- conderisation of, with benz- -- condensation-products of, 280.c_- reduction of, 253. salts, 866, 875. bromide on, 828. on, 850. hydes, 258. diuni ethylate on, 8. the ordinary temperature, 8. rivatives of, 5, 6. ate, 850. tion of, 3. and properties of, 260, 262. bromide on, 836. chloride on, 256. aldehyde, 258. Ethyl benzoylacetoacetate and its copper -- benzoylnitrosoacetate, preparation - benzoylsuccinate, decomposition- - benzoyltrimethylenecarboxylate, - dehrdrobenzoylacetate, prepara- - dibenzoylacetate, preparation of, - dtbenzoylsuccinate, action of con- -- decomposition products of, -- preparation and properties of, - ethoxpsuecinate, 866. - ethylacetoacetate, action of acetic - ethylbenzoylacetate, 841.- ethylmethylacetoacetate, 5. - fumarate. action of sodic methylate - maleate, action of sodic methylate - malonate, action of ethyl dibromo- -- action of ethylene bromide - methyl:~cetvlacetoacetate, 9. - met hylallylacetoacetate, prepara- - methylethylacetoacetate, 5. - monobenzoylsuccinate, preparation - trimethylenecai*boxylate, 81’7. - trimethylenedicarboxylate, 807. - trimeth ylenetetracarlboxylate, 8 Z . Ethyl-cetyl from ethyl and cetyl iodide., Etliyldibenzo’in, 90. Ethylene chlorothiocyanate, preparation Ethylmalonic acid, y-brom-, 814. Ethylsulphonic acid, /3-chlor-, action of primary, secondary, and tertiary mon- aininee on their respective salt3 of, 367. salt, 10. and properties of, 243. products of, 2’74.. 836, 840. tion and properties of, 283. 246, 248. centrated sulphuric acid on, 271. 265. 263. acid on the sodium salt of, 2. and el hylate on, 856, 865. and ethplate on, 867. 868. succinate on, 822. on, 80’7. tion of, 4. and properties of, 272. 40. of, 365. --- preparation of, 365. Ethyltaurine, pr~paration of, 368. Eugenol plient lcarbatnate, 777. Explosive pyrites, so-called, cause of the decrepitations in samples of, 593. F. Ferrous hydroxide, and its behaviour with nitric oxide, nitrites, and nitrates in alkaline solution, 364,.934 MDES O F SUBJECTS. Fertilisers, quick method for the esti. mation of phosphoric acid in, 185. Fil ter-papers, toughened, 183. Formocumidide, 76’1. Formortho- and para-toluidide, ’763 765. Formyl compounds derived from anilinc and homologous bases, ’162.Fulminates, non-production of oxalic acid from, and the constitution of, 7’7 Fulminurates, action of hydrochloric acid on, 7’7. Fumarates, ethereal, action of sodic alco- holates on, 855. Fumaric acid, decomposition of aromatic ethereal salts of, 899. G. Gases, dried, combustion in, 349. Glycol phenylcarbamate, 773. Green fodder, chemical alterations in, during its conversion into ensilage, 80. H. Haloyd salts, quinine test for, 210. Heptyl alcohol, preparation of, 40. Hops, presence of choline in, 298. Hydric ethyl fumsrate, 857. -- maleate, action of sodic ethylate on, 873. -methyl maleate, action of sodic inethylate on, 865. Hydrocarbon, an apparently new, from distilled Japanese petroleum, 924. Hydrocarbons, aronatic, new method of preparing, 898.- illuminzting power of, 235. - volatile, spontaneous polgmerisa- tion of, at the ordinary ~~tmospheric temperatures, 663. Hydrogen selenide, action of sulphur on, 444. - - preparation of, from iron monoselenide, 443. - - reactions of sulphurous acid with, 441. Hydroquinone phenylcarbamate, 772. Hydroxylamirie in acid solution is not >eduGblc by zinc, 612. - specific act,ion of a mixtnre of sul- phuric and nitric acids on zinc in the production of, 597. Hydroxynicotinic acid, 150. u-Hydroxypropyl phenyl ketone, 844. Hyponitrites, formation of, from nitric oxide, 361. I, Iodine, detection and estimation of, 471. Iron, colorimetric method for estimating small quantities of, 493. - monoselenirle, and the preparation of hydrogen selenide from it, 443.- sulphate, application of, in agri- culture, and its value,as a plant-food, 46. Isodinaphthyl, certain derivatives of, 104. - tetranitro- and tetramido-, 105, 106. Tsodinaphthyl-qninone, 106. Isoproppl benzoate, chlor-, preparation of, 135. J. Japanese petroleiim, distilled, an appa- rently new hydrocarbon from, 924. K. Eetones, additive and condensation com- pounds of diketones with, 11. L. Lead’ nitrososnlphate, existence of, 364. Lithium sulphate, heat of dissolution of, 98. M. Mannesium snlphate, calorimetric deter- minations of, 100. Maize, nnalyses of, 88. - fodder, analyses of, 85, 86. - quantity of nitrogen in the ensilage - silage, analyses of, 85, 86. Maleates, ethereal, action of sodic alco- Malei’c anhydride, nction of phosphorus Malto-dextrin, 560.Manit obn prairie Foils, sources of the Mercurous sulphnte, note on the pre- of, 80. holates on, 855. pentachloride on, 899. fertility of, 380, 408. paration of, 639.INDEX OF SUBJECTS. 935 Mercury, action of nitric peroxide on, - fulminate, decomposition of, foot- - vapour-preseures of, 656. Metahydroxganthraquinone, 680. Metals, certain, action of pyrosulphuric Metaxylene, description and measure- Methane, illuminating power of, 200. - preparation of, 200. Methenyldicumylamidirre, '768. Methenyldi-ortho- and para-, tolylami- Methenyldiphenylamidine, 767. Methoxynicotinic acid, 154. Methoxysuccinic acid and its salts, pro- perties of, 857, 858, 863, 871. Methyl salicylate, va.pour-pressures of, 649, 655. -- - phenylcarbamate, '7'75. Methylene chloriodide, 198.Methplphenyltaurine, preparation of, 372. Micro-organisms, chemical changes in their relation to, 159. Molecular structure of mrbon com- pounds and their absorption spectra, relation between, Part VII, 685. 631. note, 78, 7G. acid on, 636. ment of the spectrum of, 704. dine, 764, 766. N. Naphthalene, bromo-, vapour-pressures of, 650, 656. - constitution of the hnlond deriva- tives of, 497. - description and measurement of the spectrum of, 697. -- iodine-derivatives of, 518. Naphthalenes, bromiodo-, 523. - di- and tri-bromo-, derived f ~ o m - diiodo-, 521, - nitrobromo-, 506. - nitroiodo-, 519. Naphthol, bromonitro-, and some of its a-Naphthol, iodonitro-, 524. p-Naphthol, iodo-, 525. a- and P-Naphtholazobenzene-azo-a- u-Naphtholazobenzene-azo-1IJ-naphtho1, dibromonaphthylamines, 510.salts, 501. and P-naphthol, 663, 664. and its disulphonic acid (sodium salt), 664. a- and p-Naphtholazobenzene-azophenol, 665, 666. u- and b-Naphtholazobenzene-azoresor- cinol, 665, 666. p-Naphtholazobenzene-azosalicylic acid, Naphthol methyl ether, bromonitro-, Naphthols, action of diazoparanitroben- Nsphthylamine, bromonitro-, 500. Nephthylamines, bromo-, 508. - dibromo-, and their derived di- and tri- bromonaphthaleiies, 510. 8-Naphthyl cinnamate, decomposition of, by heat, 899. a- and p-Naphthyl phenylcarbamate, 776. Nicotiiiic acid, and chloro-, 151. Nitric acid, behaviour of stannous chlor- - oxide and oxygen, reaction between, -- behaviour of stannous chlo- - peroxide, liquid, constitution and Nitrification, 181. - action of gypsum in promoting, Nitrogen, the oxides of, 187.Nitrosulphates, decomposition and pro- - Pelouze's, conversion of, into hypo- Nitrosyl sulphate, preparation of, 197. Nitrous anhydride, existence of, in the -- gaseous, non-existence of, 672. Nux vomica, alkaloids of, 139. 667. 502. zene on, 661. ide towards, 633. under wzying conditions, 465. ride towards, 623. reactions of, 630. '758. perties. of, 203. nitrites and sulphites, 203. gaseous state, 457. 0. Obituary notices, 309. Orthstoiuidine hydrochloride, descrip- tion and measurement of the spectrum of, 739. Orthoxjlene, description and measure- ment of the spectrum of, 702. Oxygenous salts, some non-saturated, constitution of, and the reaction of phosphorus oxychloride with sulphites and nitrites, 205.P. Paper, action of nitric acid on, 183. Paracresyl cinnamate, decomposition of, - fumarate, 901. Paraffins, some new, 37. Paratoluidine, description and nieasure- by heat, 898. ment of the spectrum of, '74.1.936 INDEX OF SUBJECTS. Paraxylene, description and measure- Phenanthraquinone and acetone, action Phenol, action of diazoparanitrobenzene Phenolazobenzene-azophenol, 659. Phenols, polyliydric and certain mon- hydric, action of phenyl cyanate on, 770. Phenoxynicotinic acid, and the action of hydrochloric acid on it, 153. Phenyl cinnamate, 901. -- decomposition, by heat, 898. - cyanate, action of, on polyhydric and certain monhydric alcohols and phenols, ’770. ment of the spectrum of, 70’7. of potash on a mixture of, 13, 17. on, 658. - fumarate, 900. - isocyanate, action of, on formyl- and thioformyl-derivatives of aniline and its homologues, ’770.- phenjlthiocarbamate, 778. - succinate, decomposition of, by heat, 899. Phenplbenzoic acids, dibromo-, 589. P-Phenyllactic acid, formation of, from Yhenyltaurine, preparation of, 369. Phenyltaurocyamine, formation of, 373. Phloroglucol, chlorination of, 423. - trichloro-, 423. Phosphoric acid, quick method for the Phosphorus oxychloride, reaction of, Phthalic acid, monobromo-, 591. - acids, bromo-, 511. Picoline, description and measurement Piperidine, description and measure- Potassium stannite, action of nitric - sulphate, heat of dissolution of, Propane, illuminating power of, 235. - preparation of, 238. Propyl phenyl ketone, w-bromo-, 842. Propylene chlorhydrin, action of zinc ethide on the benzoate of, 134.-- constitution and oxidation of, 132, 133. - ethylphenylketate, action of hyclr- iodic and sulphuric acids on, 137. -- preparstion and oxidation of, 135, 136. - glycol, preparation of, 132. Prout’s hypothesis of the atomic weights, Pyridine derivatives, formation of, from ethyl benzoylacetate, 254. estimation of, in fertilisers, 185. with sulphites and nitrites, 205. of the spectrum of, 719. ment of the spectrum of, 731. oxide on, 362. 98. 434. nialic acid, 145. Pyridine, description and measurement of the spectrum of, 711. Pyrit,es, explosive, so-called, cause of the decrepitations in samples of, 593. Pyrocatechin phenylcarbamate, 772. Pyrogal~lol phenylcarbamate, 774. Pyrosulphuric acid, action of, on certain metals, 636.Qc Q,uinine test for non-oxylic salts, 210. Quindine, description, and measurement of the spectrum of, 722. R, Resorcind phenylcarbamate, ’7’71. - action of diazoparanitrobenzene Resorcinolazobenzene-azoresorcinol, 661. on, 660. S. Sacnharomyces, secondary forms of, foot-note, 566. Salicjl phenylcarbamate, methyl-deriva- tire of, 775. Salicylic acid, action of diazoparanitro- benzene on, 666. Selenious acid, reactions of, with hydro- gen sulphide, 441. Selenium, new and simple method for the quantitative separation of tellu- rium from, 439. - monosulphide, 446. Silicon, influence of, on the properties of cast iron, 577, 902. Silver, action of nitric peroxide on, 632. - atomic weight of, and Prout’s hy- pothesis, 434. - class of metals and their nitrites, behaviour of, towards nitric acid, 230.- fulminate, decomposition of, by hydrochloric acid, 69. - nitrite, action of nitric peroxide and of heat on, 634. Sodium fluorphosphate from soda liquors, 360. - nitrate, fused, solubility of certain salts in, 94. - orthovanadates and their aua- logues, 353. - vanadofluoride, 358. Soils, some points in the composition of, with results illustrating the sources ofINDEX OF SUBJECTS. 937 the fertility of Manitoba prairie soils, 380. Soils, various, nitrogen and carbon in, 419. Stannites, alkali, inaction of, towards ni- trites and nitrates, 363. Stannous chloride, behaviour of, towards nitric oxide and towards nitric acid, 623. Starch, is any other substance besides maltose and dextrin formed during the transformation of, by diastase ? 555.- non-crystallisable products of the action of diastase on, 52'7. Strychnine, bromo-, action of nitric acid on, 141. -- crystallography of, 144. -- physiological action of, 143. - experiments on, 139. - mono- and di-bromo- and chloro-, Sulphites, action of heat on, 208. - action of phosphorus pentachlo- ride and oxychloride on, 206, 207. - action of sulphur dioxide on, 209, 219. - constitution of, 205. - conversion of certain other salts into, by sodium, and of sulphites into other salts by chlorine or iodine, 210. 140, 141. - instability of, 212. - interrelations of, with sulphonates and sulphinates, 211. - their place in a series of sulphuryl compounds, 217. Sulphur dioxide, constitution of, 21& -- decomposition of, by dkali Sulphuric oxide, condensed, 218.sulphites, 209, 219. T. Taurine, derivatives of, Part I, 36'7. Tauriaes, mono-, di-, and tri-substituted, general method for the preparation of, 36'7. Tellurium, new and simple method for the quantitative separation of, from selenium, 439. Temperatures, constant, method for ob- taining, 640. Terebenthene from camphor oil, .and its derivatives, 782. Tetrabenzoylmethane, preparation of, 253. Tetrahydroquinoline and its hyhochlo- ride, description and measurement of the spectrum of, 731, 735. Thioformanilide and its homologues, action of heat in closed tubes on, '768. Thioformocumidide, '768. Thioformortho- and para-toluidide, 763, 765. Thioformyl compounds derived from aniline and homologous 'bases, 762. Thy my1 cinnamate, decomposition of, by heat, 899. Titanium, atomic weight of, 108. - mono- and sesqui-sulphides of, - tetrabromide, pure, preparation of, - tetrachloride, pure, preparation of, Tolane alcohol, 90. 'Toluene, formation of, from benzyl bromide, 453. Tolylbenzene, brominated dwivatives of, 586. Tribenzoylmethane, preparation and pro- perties of, 252. Tricupric sulphate, a crystalline, and crystallography of, 375,377. Trimethylene, some derivatives of, 801. Trimethylenedicarboxylic acid, action of -- and some of its salts, 810. Trimethylene methyl %ketone, 835. TrimeChylenemonocarboxylic acid and Trimethylenetetracarboxylic acid and Trimethylenelricarboxylic acid and some Trimethylsulphine, action of the halo- -- halord derivatives of, 56. !Prkethyltaurine, preparation of, 372. 491. 126. 119. hydrobromic acid on, 814. some of its salts, 815. some of its salts, 823, 824. of its salts, 823, 826. gens on the salts.of, 56. U. Urea bacillus, action of, on urea, 179. v. Vanadabs, ortho-, of sodium, and their Vapour-pressures of certain liquids, 641. -- of solids and liquids, new analogues, 353. method of determining, 42. Y. Yeast and its chemical reactions, 166.938 INDEX OF Z. Zinc, and acids, apparent influence of temperature, time, dilution, and other conditions on the reaction between, 619. - note on grannlating, foot-note, 617. SUBJECTS. Zinc, rate of action of nitric acid on, 603. - rate of action of sulphuric acid on, 598. - speci6c action of a mixture of sul- phuric and nitric acids on, in the pro- duction of hydroxylamine, 597.

ISSN:0368-1645    

DOI:10.1039/CT8854700931

出版商:RSC    

年代:1885

数据来源: RSC

摘要:

938 INDEX OF SUBJECTS. ERRATA, VOL. XLVII. Page Line 1913 38 ,, ), f:r (‘ 3246” read (‘ 32.44.” 208 16 ,? ,) ,, “ t o ” read “ at.” Zi2 14 ), top, ,, ‘( sulphates ” read (( snlphonates.” 216 7 ), bottom, ,, A read /\ . 217 4 ,, ), ,, “ chloride ” read ‘‘ chlorine.” i i 9 11 ,, top, transpose “Action of Sulphur Dzoxide on Sulphites (this 91 12 from top, “ C20H2404 ” read ((C7uH2404.” 6 ,, bottom, ,, (‘ of sulpliite ” read (‘ of sulphate.” 0 0 Ca-SO, Ctt--SO, 7 7, 1‘ 9 , “ -Sa ” read (‘ -SQO,.” vol., p. 209) ’’ to bottom of foot-note. >, 9 ,, bottom,for ‘( 20SnCl” read “ 20SnCI2.” 10 9 7 ,, ,, “ SnC1,” read ‘( SSnCl,.” 2gO 3 ,, top, ,, “ 0,t>SD02’’ read “ O,DSqo,.” On page 226, line 5 from bottom, and on page 227, line 17 from bottom, the author wishes the word (( cltrbosylamine ” to be changed to carbonylamine, and the footnote relating to them to be cancelled.225 f o r (‘ thionities ” read ‘ I thionites.” 228 11 ,, bottom, ,, “ Lossen ” reud ‘( Lossen.” 229 4 ,, top, the sentence in italics to be read as a paragraph of the 0 221 23 9 ) 9, ,, ‘(-S--” rmd “-S-.” 15 from top, text in italics, not as a sectional heading. ), 18 ,, ), f o r ‘‘ diazoammonium” read “ diazo.” Y 9 7 9 ,Y $ 9 ,, ‘( diazotammonium ” ,, ‘‘ azotammonium.” 4 ,, bottom, ,, “ nitrites ” read (( sulphites.” 2 i O 14 ,, ), ,, (‘Exuer ” ), “ Exner.” 234 2 ,, top ,, (‘ nitrites ” ,, ‘( nitrite.” 266 19 ,, ,, ,, ‘( phosphorous ’’ read “ phosphorus.” 363 15 >, 3, 9 9 < L K(J>Sn K ” 9 ) < L ,K,>sno:* 440 5 9 , i 9 ,, “ last” read “test.” 479 19 > 9 7 7 ,, ‘‘ Schmidzu” read “ Shimidzu.” 534 8 7 I 9 , ,) “ water ” read “ alcohol.” 568 ,, ,I bottom, ,, ‘( necessarily ” read “ successively.” 608 6 ,, ), ,, ‘‘ conversion ” read “ convection.” 624 5 ,, ,, ,, ‘‘ hydroxy amine ” read “ stannous chloride.” 6g2 635 7 ,, ), for ‘( nitrate ” read nitrite.” 636 19 , 9 9 9 ,, ‘‘ sulphide ” .read “ sulphite.” 7 ,, ,, ,, ‘‘ stannous chloride ” read ‘( nitric oxide.” 4 ,) top, after ‘‘ escaped ” insert (‘ the tube was sealed again sxxd left for about 18 hours.” EABBlEON AKD SONS, PBINTEBS IN OBDIBABP TO 1IEU MAJESTY, ST. MARTIN’S LABE.

ISSN:0368-1645    

DOI:10.1039/CT8854700938

出版商:RSC    

年代:1885

数据来源: RSC